The first bishop, José Jorge Torres Estans, a native of Cartagena, ruled from 30 August 1837, to 17 April 1853, when he died at the age of 81, an exile in San Antonio del Fáchira, Venezuela.

His successor, José Luis Niño, named vicar Apostolic, was consecrated in October, 1856, and also died an exile in San Antonio del Fáchira, 12 February 1864.

The third bishop, Bonifacio Antonio Toscano, governed from 13 October 1865, to his retirement in 1873.

Indalecio Barreto succeeded him 3 December 1874, and died 19 March 1875, at La Vega near Cúcuta.

The Bishop of Panamá, Ignacio Antonio Parra, his successor, ruled from 8 June 1876, until his death, 21 February 1908.