Ordinaries •
Francisco Antonio Granadillo † (22 Jun 1923 – 13 Jan 1927) •
Salvador Montes de Oca † (20 Jun 1927 – 22 Dec 1934) •
Gregorio Adam Dalmau † (29 Aug 1937 – 12 Jul 1961) •
José Alí Lebrún Moratinos † (19 Mar 1962 – 21 Sep 1972) Appointed, Coadjutor Archbishop of Caracas; future Cardinal •
Luis Eduardo Henríquez Jiménez † (9 Nov 1972 – 16 Mar 1990) •
Jorge Liberato Urosa Savino † (16 Mar 1990 – 19 Sep 2005) Appointed, Archbishop of Caracas (Cardinal in 2006) •
Reinaldo del Prette Lissot † (10 Apr 2007 – 21 November 2022) •
Jesús González de Zárate Salas (since 28 June 2024)
Auxiliary bishops •
José Joaquín Troconis Montiel (1977-1986) •
Nelson Antonio Martínez Rust (1982-1992), appointed Bishop of San Felipe •
Reinaldo del Prette Lissot † (1993-1997), appointed Coadjutor Bishop of Maracay (later returned here as Archbishop) •
José Sótero Valero Ruz † (1998-2001), appointed Bishop of Guanare
Other priests of this diocese who became bishops •
Alfredo José Rodríguez Figueroa †, appointed Auxiliary Bishop of Caracas, Santiago de Venezuela in 1974 •
Diego Rafael Padrón Sánchez, appointed Auxiliary Bishop of Caracas, Santiago de Venezuela in 1990 •
Ramón Antonio Linares Sandoval, appointed Bishop of Puerto Cabello on 1994 •
Tulio Luis Ramírez Padilla, appointed Auxiliary Bishop of Caracas, Santiago de Venezuela in 2012 ==Suffragan dioceses==