| Ordained Bishop | Years | Name | Current Title |
|---|---|---|---|
| 17 Aug 1996 | Silvano Maria Cardinal Tomasi, C.S. | Permanent Observer Emeritus to United Nations Office and Specialized Agencies in Geneva | |
| 16 Sep 2001 | Archbishop Menghesteab Tesfamariam, M.C.C.I. | Archbishop of Asmara (Eritrean) | |
| 13 Jan 2002 | Bishop Thomas Osman, O.F.M. Cap. | Bishop of Barentu (Eritrean) | |
| 3 Jul 2002 | Dominique François Joseph Cardinal Mamberti | Prefect of the Apostolic Signatura, Roman Curia | |
| 2 Mar 2003 | Bishop Kindane Yebio | Bishop of Keren (Eritrean) | |
| 18 Mar 2007 | Archbishop Leo Boccardi | Apostolic Nuncio | |
| 20 May 2012 | Bishop Fikremariam Hagos Tsalim | Bishop of Segheneity (Eritrean) | |
| 17 May 2014 | Archbishop Hubertus Matheus Maria van Megen | Apostolic Nuncio to Kenya | |
| 29 May 2016 | Bishop Angelo Pagano, O.F.M. Cap. | Vicar Apostolic of Harar, Ethiopia | |
| 25 Jul 2020 | Archbishop Luís Miguel Muñoz Cárdaba | Apostolic Nuncio to Mozambique |
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