Ordained Bishop | Years | Name | Current Title |
| Most Senior |
| 4 Sep 1966 |
| Bishop Jesús Agustín López de Lama, C.P. | Prelate Emeritus of Corocoro |
| 21 Apr 1968 |
| Archbishop René Fernández Apaza | Archbishop Emeritus of Cochabamba |
| 6 Jan 1969 |
| Bishop Abel Costas Montańo | Bishop Emeritus of Tarija |
| 6 Jan 1969 |
| Bishop Adhemar Esquivel Kohenque | Bishop Emeritus of Tarija |
| 16 Sep 1973 |
| Bishop Roger-Émile Aubry, C.SS.R. | Vicar Apostolic Emeritus of Reyes |
| 16 Jan 1977 |
| Bishop Bernardino Rivera Alvarez, O.F.M. | Auxiliary Bishop Emeritus of Potosí |
| 8 Jun 1978 |
| Julio Cardinal Terrazas Sandoval, C.SS.R. | Archbishop of Santa Cruz de la Sierra |
| 27 May 1979 |
| Archbishop Alfio Rapisarda | Apostolic Nuncio to Portugal |
| 18 Apr 1982 |
| Bishop Manuel Eguiguren Galarraga, O.F.M. | Auxiliary Bishop Emeritus of El Beni o Beni |
| 31 Jul 1982 |
| Archbishop Luis Sáinz Hinojosa, O.F.M. | Auxiliary Bishop of Cochabamba |
| 7 Jan 1984 |
| Bishop Gonzalo de Jesús María del Castillo Crespo, O.C.D. | Bishop of Bolivia, Military |
| 28 Jan 1984 |
| Bishop Luis Morgan Casey | Vicar Apostolic of Pando |
| Most Junior |
| 8 Aug 2008 |
| Bishop Adolfo Eduardo José Bittschi Mayer | Auxiliary Bishop of Sucre |
| 26 Apr 2008 |
| Archbishop Luciano Suriani | Apostolic Nuncio to Bolivia |
| 2 Sep 2007 |
| Bishop Francisco Focardi Mazzocchi, O.F.M. | Auxiliary Bishop of El Beni o Beni |
| 24 Mar 2007 |
| Bishop Jorge Herbas Balderrama, O.F.M. | Coadjutor Prelate of Aiquile |
| 30 Mar 2006 |
| Bishop Francisco Javier Del Río Sendino | Bishop of Tarija |
| 17 Sep 2005 |
| Bishop Krzysztof Bialasik, S.V.D. | Bishop of Oruro |
| 15 Sep 2005 |
| Bishop Ricardo Ernesto Centellas Guzmán | Auxiliary Bishop of Potosí |
| 25 Jul 2002 |
| Bishop Oscar Omar Aparicio Céspedes | Auxiliary Bishop of La Paz |
| 12 May 2002 |
| Archbishop Ivo Scapolo | Apostolic Nuncio to Rwanda |
| 1 Dec 2001 |
| Bishop Bonifacio Antonio Reimann Panic, O.F.M. | Vicar Apostolic of Ńuflo de Chávez |
| 13 Mar 2001 |
| Bishop Stanislaw Dowlaszewicz Billman, O.F.M. Conv. | Auxiliary Bishop of Santa Cruz de la Sierra |
| 6 Jan 2000 |
| Archbishop Józef Wesołowski | Apostolic Nuncio to Dominican Republic |