Mathews attended McKeesport Area High School, before moving on to Clemson University, where he played baseball and football.

As a senior, he was a part of another undefeated season and played in the 1951 Orange Bowl, beating the University of Miami 15–14.

[2] Mathews was selected by the Pittsburgh Steelers in the seventh round (81st overall) of the 1951 NFL draft.

He appeared in 6 games as a reserve player, while reuniting with former college teammate Fred Cone.

Early in the 1950s, he played four seasons of minor-league baseball in the St. Louis Browns farm system.