In 1987, Volpi moved with his parents from Lucca, Italy, to São Paulo. At a young age, he began his studies at the Escola Profissional Masculina do Brás. In 1911, Volpi started to paint and, in 1925, took part in his first exhibition. In the 1930s, he was part of the Grupo Santa Helena and became close to artists Ernesto de Fiori (1884-1945) and Rossi Osir (1890-1959). In 1937, he actively participated in the formation of the Sindicato dos Artistas Plásticos [Union of Plastic Artists] of São Paulo and, in the same year, he joined the FAP – Família Artística Paulista [Paulista Artistic Family].
In 1940, he won the contest promoted by IPHAN – Instituto do Patrimônio Histórico e Artístico Nacional [Institute of National Historical and Artistic Heritage], with works based on the monuments of the cities of São Miguel and Embu. His first solo exhibition took place in São Paulo, at Galeria Itá, in 1944. From the 1950s on, he began to create compositions that gradually moved towards abstraction.
In 1953, he has awarded the prize for Best National Painter at the 2nd São Paulo International Biennial – along with Di Cavalcanti –, in 1958, the Guggenheim Prize, and, in 1962 and 1966, the prize for Best Brazilian Painter by the Rio de Janeiro art critics. His recent exhibitions include Alfredo Volpi: The Poetics of Colour, at the Nouveau Musée National de Monaco (2019) and Alfredo Volpi, at Gladstone Gallery (2017). Volpi held solo shows in important institutions, among: IAC – Instituto de Arte Contemporânea (2008), Museu Oscar Niemeyer (2007), and MAM-SP – Museu de Arte Moderna de São Paulo [Museum of Modern Art of São Paulo] (2006).