It was founded as the Diocese of Caracas on June 20, 1637, and was later elevated to the rank of a metropolitan see on November 27, 1803.

This episcopal see occupies a territory of about 790 square kilometers and is not unlikely to be given several auxiliary bishops.

The most recent metropolitan archbishop had been Raúl Biord Castillo, appointed by Pope Francis on June 28, 2024.

Its cathedral episcopal see is the Catedral Metropolitana de Santa Ana, in national capital Caracas, Distrito Federal, which also has three minor basilicas: Basílica de Santa Teresa, Basílica San Pedro Apóstol and Basílica Santuario de Santa Capilla (also a national shrine).

Its ecclesiastical province in Venezuela comprises the metropolitan's own archdiocese and the following suffragan sees: