| Ordained Bishop | Years | Name | Current Title |
|---|---|---|---|
| 24 Feb 1985 | Bishop Abílio Rodas de Sousa Ribas, C.S.Sp. | Bishop Emeritus of São Tomé e Príncipe | |
| 26 Aug 1996 | Archbishop Aldo Cavalli | Apostolic Visitor (Visitator) | |
| 1 Dec 2001 | Giovanni Angelo Cardinal Becciu | Prefect Emeritus of the Congregation for the Causes of Saints, Roman Curia | |
| 17 Feb 2007 | Bishop Manuel António Mendes dos Santos, C.M.F. | Bishop Emeritus of São Tomé e Príncipe | |
| 23 Jan 2010 | Archbishop Petar Antun Rajič | Apostolic Nuncio to Italy | |
| 18 Mar 2010 | Archbishop Novatus Rugambwa | Apostolic Nuncio | |
| 17 Oct 2020 | Archbishop Giovanni Gaspari | Apostolic Nuncio to Korea | |
| 23 Jan 2022 | Bishop António Lungieki Pedro Bengui | Auxiliary Bishop of Luanda, Angola | |
| 17 Mar 2024 | Bishop João de Ceita Nazaré | Bishop of São Tomé e Príncipe | |
| 24 Aug 2024 | Archbishop Kryspin Witold Dubiel | Apostolic Nuncio to Angola |
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