Pezolt was a pupil of Johann Matthias Wurzer (1760-1838), a portrait painter in Salzburg. In 1827 he accompanied the English archeologist John Molitor on his travels through Italy. Pezolt stayed in Italy until 1837, where he lived in Florence, Pisa, Verona, and Venice. During his time in Italy he was mainly influenced by the Swiss genre painter Louis Léopold Robert (1794-1835). On a second stay in Italy, in 1840/42, he visited Rome and Sicily.
From 1842 he lived in Salzburg permanently, where he worked as a draughtsman, painter and a curator of monuments. He gained much influence on the cultural development of the city at that time. He was a co-founder of the regional art club and from 1865 responsible for the preservation of the historical monuments of Salzburg. His painting and drawing style was characterized by his interest for landscapes, history and buildings, always combined with a preference for romantic genre pictures.