Maserati was born in Voghera. In 1903 he and his brother Bindo Maserati started working for Isotta-Fraschini in Milan, on their older brother Carlo Maserati's recommendation. He followed Carlo to Bianchi in 1905, with whom he also raced and won in 1909. On Bindo's recommendation, Alfieri and Ettore Maserati went back to Isotta-Fraschini on a mission to Argentina in 1912, returning to Italy to found the new Milan-based workshop Societa Anonima Officine Alfieri Maserati in 1914.
Both served in World War I and the workshop was run by his brother Ernesto Maserati, who led a large production of spark plugs to the war effort. After the war a larger production plant was set up in Bologna.
Alfieri won a number of races in the 1920s. He died in Bologna from liver complications related to an accident in 1928.
He was commemorated in the "Maserati Alfieri" concept car, presented in 2014 for the 100-year anniversary of Maserati.