| Librarian: |   Archbishop Angelo Vincenzo Zani (75) (2022.09.26 – 2025.03.28) |
| Librarian: |   Cardinal José Tolentino Calaça de Mendonça (59) (2018.09.01 – 2022.09.26) |
| Librarian: |   Archbishop Jean-Louis Bruguès, O.P. (81) (2012.06.26 – 2018.09.01) |
| Librarian: |  Cardinal Raffaele Farina, S.D.B. (91) (2007.06.25 – 2012.06.09) |
| Librarian: | Cardinal Jean-Louis Tauran (2003.11.24 – 2007.06.25) |
| Librarian: |  Cardinal Jorge María Mejía (1998.03.07 – 2003.11.24) |
| Librarian: | Cardinal Luigi Poggi (1994.11.29 – 1997.11.25) |
| Librarian: |  Cardinal Antonio María Javierre Ortas, S.D.B. (1988.07.01 – 1992.01.24) |
| Librarian: |  Cardinal Alfons Maria Stickler, S.D.B. (1985.05.27 – 1988.07.01) |
| Librarian: | Cardinal Antonio Samorè (1974.01.25 – 1983.02.03) |
| Librarian: | Cardinal Eugène-Gabriel-Gervais-Laurent Tisserant (1957.09.14 – 1971.03.27) |
| Librarian: | Cardinal Giovanni Mercati (1936.06.18 – 1957.08.23) |
| Librarian: |  Cardinal Franziskus Ehrle, S.J. (1929.04.17 – 1934.03.31) |
| Librarian: |  Cardinal Francis Aidan Gasquet, E.B.C. (1919.05.09 – 1929.04.05) |
| Librarian: | Cardinal Francesco di Paola Cassetta (1914.01.03 – 1919.03.23) |
| Librarian: | Cardinal Mariano Rampolla del Tindaro (1912.11.26 – 1913.12.16) |
| Librarian: | Cardinal Placido Maria Schiaffino, O.S.B. Oliv. (1889.02.20 – 1889.09.23) |
| Librarian: | Cardinal Jean-Baptiste-François Pitra, O.S.B. (1869.01.19 – 1875.03.15?) |
| Librarian: | Cardinal Antonio Tosti (1860.01.13 – 1866.03.20) |
| Librarian: | Cardinal Angelo Mai (1853.06.27 – 1854.09.09) |
| Librarian: | Cardinal Luigi Lambruschini, B. (1834.12.11 – 1853.06.27) |
| Librarian: | Cardinal Giuseppe Albani (1830.04.23 – 1834.12.03) |
| Librarian: | Cardinal Giulio Maria Della Somaglia (1826.10.01 – 1830.04.02) |
| Librarian: | Cardinal Ercole Consalvi (1814.05.17 – 1823.09.20) |
| Librarian: | Cardinal Luigi Valenti Gonzaga (1802.01.12 – 1808.12.29) |
| Librarian: | Cardinal Ercole Consalvi (1801.12.19 – 1806.06.17) |
| Librarian: | Cardinal Francesco Saverio De Zelada (1779.12.15 – 1801.12.19) |
| Librarian: | Cardinal Alessandro Albani (1761.08.12 – 1779.12.11) |
| Librarian: | Cardinal Domenico Silvio Passionei (1755.01.22 – 1761.07.05) |
| Librarian: | Cardinal Angelo Maria Quirini, O.S.B. Cas. (1730.09.04 – 1755.01.06) |
| Librarian: | Cardinal Benedetto Pamphili, O.E.S.S.H. (1704.02.26 – 1730.03.22) |
| Librarian: | Cardinal Enrico Noris, O.E.S.A. (1700.03.06 – 1704.02.23) |
| Librarian: | Cardinal Girolamo Casanate (1693.12.02 – 1700.03.03) |
| Librarian: | Cardinal Francesco Lorenzo Brancati di Lauria, O.F.M. Conv. (1681.09.19 – 1693.11.30) |
| Librarian: | Cardinal Flavio Chigi (1659.06.21 – 1681) |
| Librarian: | Cardinal Luigi Capponi (1649.08.04 – 1659.04.06) |
| Librarian: | Cardinal Orazio Giustiniani, C.O. (1646.09.25 – 1649.07.25) |
| Librarian: | Cardinal Antonio Marcello Barberini, O.F.M. Cap. (1633.12.13 – 1646.09.11) |
| Librarian: | Cardinal Francesco Barberini (1626.07.01 – 1633.12.13) |
| Librarian: | Cardinal Scipione Cobelluzzi (1618.02.17 – 1626.06.29) |
| Librarian: | Cardinal Scipione Caffarelli-Borghese (1609.06.11 – 1618) |
| Librarian: | Cardinal Ludovico de Torres (1607.07.04 – 1609.07.08) |
| Librarian: | Cardinal Cesare Baronio, C.O. (1597.05 – 1607.06.30) |
| Librarian: | Cardinal Marco Antonio Colonna (1591 – 1597.03.13) |
| Librarian: | Cardinal William Allen (1590 – 1594.10.16) |
| Librarian: | Cardinal Antonio Carafa (1585.10.06 – 1591.01.13) |
| Librarian: | Cardinal Guglielmo Sirleto (1572.03.18 – 1585.10.06) |
| Librarian: | Cardinal Alfonso Carafa (1559 – 1565.08.29?) |
| Librarian: | Cardinal Roberto de’ Nobili (1555? – 1559.01.18) |
| Librarian: | Cardinal Marcello Cervini (later Pope Marcellus II) (1550.05.24 – 1555.04.09) |
| Librarian: | Cardinal Gerardo Caccianemici dall’Orso, C.R.S.M.R. (later Pope Lucius II) (1141 – 1144.03.09) |
| Librarian: | Cardinal Aymery de la Châtre, C.R.L. (1125.02 – 1141.05.28) |
| Librarian: | Saint Cardinal Bruno di Segni, O.S.B. (1086 – 1123.07.23) |
| Librarian: | Saint Cardinal Gregorio Ostiense, O.S.B. (1034? – 1044.05.09) |
| Pro-Librarian: | Cardinal Luigi Poggi (1992.04.09 – 1994.11.29) |
| Pro-Librarian: | Cardinal Alfons Maria Stickler, S.D.B. (1983.09.07 – 1985.05.27) |
| Pro-Librarian: | Archbishop Domenico Maria Jacobini (later Cardinal) (1880.11.16 – 1882.03.30) |
| Pro-Librarian: | Cardinal Domenico Silvio Passionei (1741.07.10 – 1755.01.22) |
| Prefect: | Msgr. Cesare Pasini (2007.06.25 – 2023.02.14) |
| Prefect: | Bishop Raffaele Farina, S.D.B. (91) (later Cardinal) (1997.05.25 – 2007.06.25) |
| Prefect: | Fr. Leonard E. Boyle, O.P. (1984 – 1997) |
| Prefect: | Fr. Alfons Maria Stickler, S.D.B. (later Cardinal) (1971 – 1983.09.07) |
| Prefect: |  Fr. Alfonso Raes, S.J. (1962 – 1971) |
| Prefect: | Fr. Joaquín Anselmo María Albareda, O.S.B. Subl. (later Cardinal) (1936 – 1962.03.19) |
| Prefect: | Cardinal Giovanni Mercati (? – 1936.06.18) |
| Prefect: | Msgr. Achille Ratti (later Pope Pius XI) (1915? – 1919.07.03) |
| Pro-Prefect: | Fr. Eugène-Gabriel-Gervais-Laurent Tisserant (later Cardinal) (1925? – 1930?) |
| Vice-Prefect: |  Dr. Timothy James Janz (2020.04.20 – 2025.04.02) |
| Vice-Prefect: | Dr. Ambrogio M. Piazzoni (1999.03.11 – 2020) |
| Vice-Prefect: | Msgr. Paul Canart (1994 – 1997) |
| Vice-Prefect: | Msgr. José Ruysschaert (1965 – 1984) |
| Vice-Prefect: | Fr. Arnoldo van Lantschoot, O. Praem. (1951 – 1965) |
| Vice-Prefect: | Msgr. Roberto Devreesse (1945 – 1950) |
(x 5)
Fr. Mauro Mantovani, S.D.B. (59)