| Villain | First appearance | Description |
| Aquarius | Justice League of America #73 | A living star who had been on trial for their crimes by other living stars and sentenced to wandering the multiverse. He despised order and tried to upset the universe, but had lost most of his power in that way, only having about enough to survive by the star's judgement. Was responsible for the death of Larry Lance and in effect, Black Canary's move from Earth-One to Earth-Two. |
| Auntie Gravity | World's Finest Comics #261 | An elderly woman who developed anti-gravity powers. Forming a gang with her three nephews, she menaced Star City before being defeated by Black Canary. |
| Banko Jim | Flash Comics #90 | A bank robber who created an elaborate scheme to frame Black Canary for murder after Johnny Thunder snapped a picture of him committing a crime. |
| Big Game | Green Arrow and Black Canary #23 | The name of two villains, the first a retroactive early opponent of Green Arrow that hunted the hero and was murdered by Cupid years later. His son Blake took up the torch. |
| Blazing Infernos | Green Lantern #100 | A Star City street gang, the Infernos set off bombs throughout the city and were secretly funded by insurance investors hoping to justify raised rates. Green Arrow, Black Canary, and Roy Harper caught the Infernos, who turned informant on the investors. |
| Bonfire | Detective Comics #553 | A pyrokinetic villainess. |
| Borch | Green Lantern #110 | An extradimensional vagabond whose careless travel into the "Silver Twist" cosmic rift discharged energy that almost detonated a nuclear-powered satellite in Earth's orbit. Green Arrow and Green Lantern entered the twist to find Borch had discovered/created "Coyote Gulch", a reality based on the American Old West, and was leading the Clancy Bunch to take over the Gulch. Green Arrow defeated the Clancy Bunch, while Green Lantern defeated Borch. |
| Bullet Ben | Flash Comics #93 | A petty crook disguised as a swami and leader of the Order of the Crimson Crystal cult. |
| Colonel Krisp | Green Lantern #94 | A renegade military officer, Thaddeus Lucius Krisp abducted Black Canary in a failed attempt to extort Green Arrow into assassinating the President of the United States. |
| Discord | Green Arrow and Black Canary #17 | Sonic-powered criminal Sean Sonus temporarily rendered Star City's inhabitants deaf before being defeated. |
| Dodger | Green Arrow and Black Canary #7 | A high-tech supercriminal working in England. |
| Doomsters | Justice League of America #78 | By the time the pollutant-ridden planet Monsan finally became uninhabitable, a handful of survivors had altered their body chemistries to enable them to thrive on pollutants, with the unanticipated effect of warping their minds so that they sought to render other planets equally polluted. These survivors, the Doomsters, led by Chokh, came to Earth intent on converting its atmosphere into a gas which they alone could breathe; they defeated Black Canary and other JLA members, but Green Arrow rescued the heroes, ultimately allowing the JLA sufficient recovery time to defeat the Doomsters. Green Arrow and Black Canary's romance first developed in the wake of this crisis, making it of particular relevance in both characters' histories. |
| Dregz | Green Arrow and Black Canary #15 | Machete-wielding street thug and supervillain wannabe. |
| Duchess | Flash Comics #94 | A criminal mastermind who disguised herself as a flower girl to assassinate people and used a "photon smasher" flashlight to blast enemies. |
| el Espectro | Green Lantern #120 | In 1513, Spaniard Jaime Sanchez discovered Florida's Fountain of Youth, but was betrayed and buried alive by his fellow explorers; uprooted almost 500 years later, he fought Green Arrow and Black Canary before being defeated by Green Lantern. |
| Glorn Hive-Master | World's Finest Comics #253 | The leader of the extradimensional Glorn race, who abducted Black Canary to be their queen, pursued by Green Arrow, devolved into harmless state via radio waves. |
| Harpy | Green Lantern #82 | The leader of a race of mythical bird-women, the Harpy first battled Black Canary, Green Arrow and Green Lantern under the control of the Witch Queen; a Korugarian sorceress and sister of Sinestro. The Harpy later returned as a member of the Anti-Justice League as Black Canary's counterpart, teaming up with Merlyn to capture Green Arrow and Black Canary. |
| Hellgrammite | The Brave and the Bold #80 | After mutating himself into insectlike form, Roderick Rose clashed with several super-heroes, including Green Arrow and Black Canary in World's Finest Comics #248-249; he eventually became more commonly associated with Superman. |
| Huntress | Sensation Comics #68 | A big-game hunter and tiger-themed criminal, Huntress is both the archenemy of the second Black Canary's mentor Wildcat and one-time foe of the first Black Canary and her then-boyfriend Starman. |
| Huntress of the Highway | Flash Comics #92 | A criminal who sent a funeral wreath to Larry Lance as a threat and set up a truck route that would trap trucks and steal their cargo, before being foiled by Black Canary and Larry. |
| Jakob Whorrsman | Black Canary #1 | Corporate mogul who uses his powerful connections and monetary resources for various evil deeds. |
| Joshua | Green Lantern #78 | Mind-controlling leader of cult preparing for race war, brainwashed Black Canary into almost killing Green Arrow; cult later taken over by Sister Joshua, who battled Black Canary, but not Green Arrow. |
| Miss Masters | Flash Comics #95 | A woman who disguised herself as Black Canary to murder her uncle and inherit his fortune. |
| Mist | Adventure Comics #67 | A criminal mastermind who can transform into living mist. The Mist battled Black Canary during her time dating the Mist's archenemy Starman. |
| Mrs. Hollinger | World's Finest Comics #282 | Harbored vendetta against Green Arrow for accidentally killing her hoodlum son when the latter's gang attacked the hero ; hired Slingshot and gang to abduct Black Canary, then replace Green Arrow's stunt arrows with lethal arrows so he would again inadvertently kill and presumably retire; outsmarted by Green Arrow, declared vengeance against him to be her only reason left to live. |
| Onomatopoeia | Green Arrow #12 | Making sport of slaying costumed heroes, the enigmatic Onomatopoeia tried to kill Black Canary and the Arrow family. |
| Order of the Crimson Crystal | Flash Comics #93 | A cult of women obsessed with obtaining a "mystical" crimson ruby given to Black Canary by a dying woman. |
| Pete Lomax | Detective Comics #549 | After getting his hands on a bow and arrow, Pete Lomax tracks down Green Arrow and Black Canary and puts the latter in the hospital. |
| Pistolera | Detective Comics #674 | A sharp-shooting assassin. Part of a group of assassins called the Ravens, charged with taking out Black Canary and the Birds of Prey. |
| Sniper One | Green Arrow and Black Canary #11 | Formerly employed by the mysterious Echo Initiative group, psychologically unstable assassin Palmer Cokes was hired by Shado to kill Green Arrow, but ultimately failed. |
| Socks Slade | Flash Comics #88 | A gangster who stole the famous Kooblin Sapphire and was foiled by Black Canary and Johnny Thunder. |
| Thurston Keane | Action Comics #450 | Member of the Organization, a subversive group equipped with nuclear weapons and intent on "neutralizing" the world's governments; posed as vacation resort manager; his attempt to pin murder charges on vacationing Green Arrow and Black Canary led to the investigation, and presumed destruction, of the Organization. |
| Dr. Titus Selinger | DC Comics Presents #54 | Scientist whose attempt to harness outer space rays created deadly smog across the U.S., as well as a giant smog-creature; Green Arrow and Black Canary worked with Superman to restore things to normal. |
| Witch Queen | Green Lantern #82 | Alleged sister of Sinestro, commanded Harpies and Amazon warriors in a war against all men; fought Green Arrow, Black Canary, and Green Lantern. |
| Wizard | All Star Comics #34 | Member of the Injustice Society, the Wizard fought the first Black Canary on a few occasions both on her own and with the Justice Society. He eventually cursed her daughter with a potent sonic cry. |
| Yellow Peril | Green Lantern #107 | Quintet of skyjackers who planned to take over Coast City's airport and, anticipating trouble from Green Lantern, dressed themselves in yellow costumes which rendered them immune to Green Lantern's power ring. However, they did not anticipate the presence of Green Arrow and Black Canary, who easily defeated them sans power rings. |