Monsignor Larrea Holguín was a professor in various Ecuadorian universities, including the Catholic University of Guayaquil of and Central University of Ecuador.
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Aside from his political functions Montalvo was a professor of law at the Central University of Ecuador and the Rector of the Colegio Nacional Mejía.
From an early age he was very interested in art and as a young man he studied painting at the Central University in Quito.
In 1936 he went into exile because of his criticism of Francisco Franco, traveling first to Ecuador, where he taught at the Central University of Ecuador (1939–42) where he became a close friend with the writer Alfredo Pareja Diezcanseco, then to México, where he taught at the UNAM (1942–46) and finally establishing in Venezuela in 1946 and becoming a Venezuelan citizen in 1952.
He began his education as a student of architecture at the Central University of Quito in 1951.