He was the son of Spaniard Juan Pío de Montúfar y Frasso, first Marquis of Selva Alegre and President of the Royal Audiencia of Quito from 1753 to 1761.
He became inspired by the ideas of Enlightenment and a friend of Eugenio Espejo, Antonio Nariño, Francisco José de Caldas, and Manuela Cañizares.
On 10 August 1809, a group of Criollo Revolutionary intellectuals in the city of Quito deposed the Spanish ruler Manuel Ruiz Urriés de Castilla, and formed a provisional Junta, of which he became president.
This event is known in Ecuador and other countries in the region as the First Cry of Hispanic American Independence, because it constituted the beginning of the emancipation process of Latin America.
Montúfar informed José Fernando de Abascal y Sousa, Viceroy of Peru of his willingness to work for the restoration of the legitimate Government.