He attended Toledo Macomber High School in Toledo, where he led the team to the 1964 City League championship. Mayes attended The Ohio State University and was a starting lineman for all 28 games he played for the Ohio State Buckeyes.
His first two years, he was a tight education After the Buckeyes had records of 4-5 and 6-3, respectively, in his first two season, in his senior year he was switched to offensive tackle. Following his senior season, Mayes was named Second-Team All-American by the Associated Press.
Mayes was selected in the first round (14th overall) of the 1969 NFL Draft by the Chicago Bears, for whom he played one season and 13 games.
In January 1970, he was traded by the Bears to the Cincinnati Bengals in return for defensive lineman Bill Staley and Harry Gunner. In 2004, the Chicago Tribune rated the trade of Mayes by the Bears to the Bengals the sixth-worst in Bears history.
Mayes" first season with the Bengals, 1970, was the Bengals" first in the NFL following the NFL/American Federation of Labor-Congress merger. He proceeded to become a perennial starter at offensive left tackle for eight seasons with the Bengals.
During his eight-year Bengals career, Mayes started 98 of the 110 games he played.
He played out his option and became a free agent. In June 1978, he signed with the Philadelphia Eagles, for whom he played his final NFL season. As a backup, he played in all 16 games.