He played an important role during the reign of King Afonso V of Portugal, when he was appointed Chancellor of the Kingdom.
They had two sons and four daughters: When King John II of Portugal succeeded on the throne of Portugal and started his fight against the high aristocracy, namely the Braganzas, Dom Álvaro tried an approach with the King, but he was unsuccessful; his older brother, Ferdinand II, 3rd Duke of Braganza was executed, the family estates were confiscated, and the remaining family (Álvaro included) exiled to Castile.
Queen Isabella I granted Dom Álvaro important estates in Gelves, and he was appointed Mayor of Seville and Andújar.
He also took part in the conquest of the Kingdom of Granada led by the Catholic Monarchs.
Álvaro of Braganza died in Toledo and his body was later transferred to the Convent of St. John Evangelist, in Évora.