| Diplomatic accreditation | Ambassador | Observations | List of prime ministers of Italy | Prime Minister of Bulgaria | Term end |
|---|
| July 3, 1879 | Domenico Brunenghi | Agent and consul general with letter of credentials | Benedetto Cairoli | Todor Burmov | |
| February 9, 1880 | Renato De Martino | March 6, 1898 Italian ambassador to China [ it ] | Benedetto Cairoli | Dragan Tsankov | |
| January 24, 1884 | Carlo Alberto Gerbaix de Sonnax | | Agostino Depretis | Petko Karavelov | |
| June 29, 1893 | Alessandro Riva | | Francesco Crispi | Stefan Stambolov | |
| November 24, 1895 | Giulio Silvestrelli | | Francesco Crispi | Konstantin Stoilov | |
| August 9, 1901 | 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. [2] | Giuseppe Zanardelli | Petko Karavelov | November 9, 1902 |
| May 12, 1903 | Guglielmo Imperiali | 1891 Marquis Guglielmo Imperiali di Francavilla, head of the Italian Legation in Washington, D.C., Chargé d'affaires of the Italian ambassador to the United States [ it ] [3] | Giovanni Giolitti | Racho Petrov | |
| March 31, 1904 | Fausto Cucchi Boasso | agent and consul general letter of credentials | Giovanni Giolitti | Racho Petrov | |
| May 6, 1909 | Fausto Cucchi Boasso | extraordinary envoy and plenipotentiary minister, with letter of credentials | Sidney Sonnino | Aleksandar Malinov | |
| June 23, 1910 | Alessandro De Bosdari [ it ] | From 1922 to 1926 he was Italian ambassador to Germany [ it ] | Luigi Luzzatti | Aleksandar Malinov | |
| February 23, 1913 | Fausto Cucchi Boasso | | Giovanni Giolitti | Stoyan Danev | |
| September 14, 1920 | Luigi Aldrovandi Marescotti | | Francesco Saverio Nitti | Aleksandar Stamboliyski | |
| January 22, 1923 | 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 | |
| May 26, 1926 | Renato Piacentini | Mussolini inviò Amadori a Riga, sostituendolo con il ministro a Riga, Renato Piacentini | Benito Mussolini | Andrey Lyapchev | |
| January 29, 1931 | Giuliano Corà | extraordinary envoy and plenipotentiary minister, with letter of credentials | Benito Mussolini | Aleksandar Malinov | |
| December 31, 1934 | Giuseppe Sapuppo | extraordinary envoy and plenipotentiary minister | Benito Mussolini | Kimon Georgiev | |
| October 27, 1937 | Giuseppe Talamo Atenolfi | | Benito Mussolini | Georgi Kyoseivanov | |
| January 29, 1940 | Massimo Magistrati | | Benito Mussolini | Georgi Kyoseivanov | |
| June 7, 1943 | Francesco Giorgio Mameli | extraordinary envoy and plenipotentiary minister | Pietro Badoglio | Dobri Bozhilov | |
| September 21, 1945 | Piero Vinci [ it ] | Chargé d'affaires | Ferruccio Parri | Kimon Georgiev | |
| December 14, 1958 | Giovanni-Battista Guarnaschelli | extraordinary envoy and plenipotentiary minister | Amintore Fanfani | Anton Yugov | |
| January 22, 1952 | Gastone Rossi Longhi | 1960: Ambasciatore d'ltaiia ¡n Lima | Ferruccio Parri | Valko Chervenkov | |
| April 27, 1955 | Filippo Muzi Falconi | | Antonio Segni | Valko Chervenkov | |
| December 16, 1958 | Roberto Gaja [ it ] | | Amintore Fanfani | Anton Yugov | |
| February 26, 1963 | Orazio Antinori di Castel San Pietro Aquae Ortus | extraordinary envoy and plenipotentiary minister | Giovanni Leone | Todor Zhivkov | |
| September 2, 1964 | Orazio Antinori di Castel San Pietro Aquae Ortus | Ambassador | Giovanni Leone | Todor Zhivkov | |
| April 7, 1968 | Giuseppe Puri Purini [ de ] | | Giovanni Leone | Todor Zhivkov | |
| January 13, 1972 | Franz Cancellario d'Alena | Franz Cancellario d'Alena ist am 16. Januar 1957 das Exequatur der Bundesregierung erteilt worden. | Giulio Andreotti | Stanko Todorov | |
| January 10, 1979 | Franz Cancellario d'Alena | | Francesco Cossiga | Stanko Todorov | |
| June 9, 1980 | Carlo Maria Rossi Arnaud | | Francesco Cossiga | Stanko Todorov | |
| April 9, 1984 | Giovanni Battistini | | Bettino Craxi | Grisha Filipov | |
| November 21, 1987 | Paolo Tarony | | Amintore Fanfani | Georgi Atanasov (politician) | |
| February 12, 1990 | Agostino Mathis | | Giulio Andreotti | Andrey Lukanov | |
| June 24, 1994 | Stefano Rastrelli | | Silvio Berlusconi | Reneta Indzhova | |
| October 31, 1996 | Tommaso Troise | | Romano Prodi | Zhan Videnov | |
| April 28, 1999 | Alessandro Grafini | | Massimo D’Alema | Ivan Kostov | |
| May 9, 2003 | Giovan Battista Campagnola | | Silvio Berlusconi | Simeon Sakskoburggotski | |
| May 16, 2008 | Stefano Benazzo | | Silvio Berlusconi | Sergei Stanishev | |
| September 3, 2012 | Marco Conticelli | | Mario Monti | Boyko Borisov | |
| September 19, 2016 | Stefano Baldi | | Matteo Renzi | Boyko Borisov | January 2, 2021 |
| January 5, 2021 | Giuseppina Zarra | | Mario Draghi | Boyko Borisov | October 22, 2022 |