| Ordained Bishop | Years | Name | Current Title |
|---|---|---|---|
| 5 Nov 1977 | Archbishop Blasco Francisco Collaço | Apostolic Nuncio | |
| 31 Jul 1988 | Bishop Georgi Ivanov Yovchev | Bishop of Sofia e Plovdiv | |
| 22 Sep 1990 | Archbishop Giuseppe Leanza | Apostolic Nuncio | |
| 6 Jan 1994 | Bishop Christo Proykov | Bishop Emeritus of Saint John XXIII of Sofia (Bulgarian) | |
| 12 Sep 2000 | Archbishop Antonio Mennini | Official of the Secretariat of State, Roman Curia | |
| 11 Jan 2004 | Archbishop Anselmo Guido Pecorari | Apostolic Nuncio | |
| 26 Apr 2008 | Archbishop Luciano Suriani | Apostolic Nuncio to Bulgaria | |
| 17 Jan 2021 | Bishop Rumen Ivanov Stanev | Auxiliary Bishop of Sofia e Plovdiv | |
| 19 Mar 2021 | Bishop Strahil Veselinov Kavalenov | Bishop of Nicopoli | |
| 6 Jul 2024 | Bishop Petko Valov | Bishop of Saint John XXIII of Sofia (Bulgarian) |
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