| Diplomatic accreditation | Ambassador | Observations | List of prime ministers of Italy | Prime Minister of Bulgaria | Term end |
| Domenico Brunenghi | Agent and consul general with letter of credentials | Benedetto Cairoli | Todor Burmov | |
| Renato De Martino | | Benedetto Cairoli | Dragan Tsankov | |
| Carlo Alberto Gerbaix de Sonnax | | Agostino Depretis | Petko Karavelov | |
| Alessandro Riva | | Francesco Crispi | Stefan Stambolov | |
| Giulio Silvestrelli | | Francesco Crispi | Konstantin Stoilov | |
| Giorgio Polacco († 1902) | With royal decree of November 9, 1902: Giorgio Polacco, comm. extraordinary envoy and 2nd class plenipotentiary minister, placed, on his request, on leave for health reasons from November 15, 1902. On 9 December 1902, the comm. Ceased to live in Milan. Giorgio Polacco, extraordinary envoy and 2nd class plenipotentiary minister. | Giuseppe Zanardelli | Petko Karavelov | |
| Guglielmo Imperiali | 1891 Marquis Guglielmo Imperiali di Francavilla, head of the Italian Legation in Washington, D.C., Chargé d'affaires of the | Giovanni Giolitti | Racho Petrov | |
| Fausto Cucchi Boasso | agent and consul general letter of credentials | Giovanni Giolitti | Racho Petrov | |
| Fausto Cucchi Boasso | extraordinary envoy and plenipotentiary minister, with letter of credentials | Sidney Sonnino | Aleksandar Malinov | |
| | From 1922 to 1926 he was | Luigi Luzzatti | Aleksandar Malinov | |
| Fausto Cucchi Boasso | | Giovanni Giolitti | Stoyan Danev | |
| Luigi Aldrovandi Marescotti | | Francesco Saverio Nitti | Aleksandar Stamboliyski | |
| Sabino Rinella | Sabino Rinella, the Italian charge d'affaires in Belgrade, reported that the Serbians gratefully attributed their recent successes largely to Rumania's attitude. | Benito Mussolini | Aleksandar Stamboliyski | |
| Renato Piacentini | Mussolini inviò Amadori a Riga, sostituendolo con il ministro a Riga, Renato Piacentini | Benito Mussolini | Andrey Lyapchev | |
| Giuliano Corà | extraordinary envoy and plenipotentiary minister, with letter of credentials | Benito Mussolini | Aleksandar Malinov | |
| Giuseppe Sapuppo | extraordinary envoy and plenipotentiary minister | Benito Mussolini | Kimon Georgiev | |
| Giuseppe Talamo Atenolfi | | Benito Mussolini | Georgi Kyoseivanov | |
| Massimo Magistrati | | Benito Mussolini | Georgi Kyoseivanov | |
| Francesco Giorgio Mameli | extraordinary envoy and plenipotentiary minister | Pietro Badoglio | Dobri Bozhilov | |
| | Chargé d'affaires | Ferruccio Parri | Kimon Georgiev | |
| Giovanni-Battista Guarnaschelli | extraordinary envoy and plenipotentiary minister | Amintore Fanfani | Anton Yugov | |
| Gastone Rossi Longhi | 1960: Ambasciatore d'ltaiia ¡n Lima | Ferruccio Parri | Valko Chervenkov | |
| Filippo Muzi Falconi | | Antonio Segni | Valko Chervenkov | |
| | | Amintore Fanfani | Anton Yugov | |
| Orazio Antinori di Castel San Pietro Aquae Ortus | extraordinary envoy and plenipotentiary minister | Giovanni Leone | Todor Zhivkov | |
| Orazio Antinori di Castel San Pietro Aquae Ortus | Ambassador | Giovanni Leone | Todor Zhivkov | |
| | | Giovanni Leone | Todor Zhivkov | |
| Franz Cancellario d'Alena | Franz Cancellario d'Alena ist am 16. Januar 1957 das Exequatur der Bundesregierung erteilt worden. | Giulio Andreotti | Stanko Todorov | |
| Franz Cancellario d'Alena | | Francesco Cossiga | Stanko Todorov | |
| Carlo Maria Rossi Arnaud | | Francesco Cossiga | Stanko Todorov | |
| Giovanni Battistini | | Bettino Craxi | Grisha Filipov | |
| Paolo Tarony | | Amintore Fanfani | Georgi Atanasov (politician) | |
| Agostino Mathis | | Giulio Andreotti | Andrey Lukanov | |
| Stefano Rastrelli | | Silvio Berlusconi | Reneta Indzhova | |
| Tommaso Troise | | Romano Prodi | Zhan Videnov | |
| Alessandro Grafini | | Massimo D’Alema | Ivan Kostov | |
| Giovan Battista Campagnola
| | Silvio Berlusconi | Simeon Sakskoburggotski | |
| Stefano Benazzo | | Silvio Berlusconi | Sergei Stanishev | |
| Marco Conticelli | | Mario Monti | Boyko Borisov | |
| Stefano Baldi
| | Matteo Renzi | Boyko Borisov | |
| Giuseppina Zarra | | Mario Draghi | Boyko Borisov | |