Diego Bautista Urbaneja, a Minister of Foreign Affairs, was designated as the first director.

The library contains several special collections: According to their website, "The institution aspires to be an active organization in the generation of knowledge through the publication of various titles, printed or virtual, specialized or of collective interest, which are a contribution to the formation of a citizenry committed to building a better society.

"[4] In 1831 Interior Secretary Antonio Leocadio Guzmán proposed the idea of merging convent libraries and books that were previously scattered throughout the country.

"[6] In 1874 president Antonio Guzmán Blanco mandated that the collections of the convent libraries were to be delivered to the Universidad Central de Venezuela.

These collections would ultimately be added to the National Library, then located in the university campus.