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Castiglione returned to home in January 1946 and played for the Selma Cloverleafs of the Class B Southeastern League that year. Following a strong season in which he batted .342 with 81 RBIs, he moved up to the Indianapolis Indians of the Class AAA American Association for 1947, and was called up by the Pirates in September.

Castiglione made his major league debut on September 10, 1947. He appeared in 13 games and hit .250. He was back with Indianapolis for 1948, but after another strong year in which he batted .308 with 88 RBIs, he secured his place with the Pirates.

Castiglione spent the next four-and-a-half years in Pittsburgh as a utility infielder. His best season was 1951, when he played 132 games and batted .261 with 42 RBIs.

At 32, he was traded to the St. Louis Cardinals in June 1953, where he ended his major league career the following year. Castiglione continued to play in the minors until 1958 with Toronto, Buffalo, Binghamton and Little Rock.

Pete Castiglione moved to Pompano Beach, Florida, where he became a letter carrier for the Postal Service. He always kept active in the sports community, refereeing and umpiring. He also acted as a scout for the Pirates, and wrote a column for the Pompano Town News. In 1967 he coached the Cardinal Gibbons High School baseball team to a fifth place finish in the state. He also coached the American Legion team.