Martino and four of his brothers--Albert, Ernest, Giovanni and Edmund--worked in a commercial art studio in Philadelphia founded by their father, Carmine Martino, a mason and stonecutter who had come to this country from his native Italy. Antonio began his art studies at the age of thirteen at the Graphic Sketch Club and by fifteen had apprenticed himself to a lithographic company. He took further classes at several other Philadelphia institutions: the Spring Garden Institute, the Philadelphia Museum School of Industrial Arts, and the La France Art Institute. His most influential teacher was Albert Jean Adolphe who had studied in Paris under Jean Leon Gerome. An important break came for Martino when, in 1926, he won a Bronze Medal at the Sesquicentennial International Exhibition in Philadelphia. That same year, he began exhibiting his works at the National Academy and remained a consistent participant in the Academy's annuals for the rest of his life. He also was a consistent award winner at the Academy, earning his first such honor with the Murphy Memorial Prize in 1926. He also won the Academy's First Hallgarten Prize (1927 and 1937), the Saltus Medal (1964), the Altman Prize (1966), and the Truman Prize (1981).
Martino was principally a landscape painter. He was fascinated with the industrial towns on and near the Schuylkill River. His favorite spots included the banks of Darby Creek and the Delaware River near New Hope, Pennsylvania, and especially the area around Manayunk, a favorite of a number of Pennsylvania impressionists, which Martino discovered in the 1930s. He especially liked to paint winter landscapes in the area, using an impressionist brushstroke and often painting out of doors.
In 1941, Martino and one of his brothers started an advertising art business. He was a member of the National Arts Club and the American Watercolor Society which honored him with a Dolphin Fellowship. At the National Academy, he served on juries in 1944, 1947, 1954, 1962, and 1970.
In 1971 he moved to Thousand Oaks, California. A retrospective of his work was held at the Woodmere Art Gallery (1982).