Doleman played football collegiately at the University of Pittsburgh. He was a star linebacker and defensive end for the Pitt Panthers from 1982 to 1984. He ended his career at Pitt with 25 sacks which was good for 3rd All-time at the time of his departure. That total still ranks 6th all-time in Pitt annals.
Doleman is a member of Alpha Phi Alpha, the first intercollegiate Greek-letter fraternity established for African Americans.
Doleman was selected by the Minnesota Vikings in the 1st round (4th overall) of the 1985 NFL Draft and began his NFL career as an outside linebacker in the Vikings 3-4 defense. However, the team switched to a 4-3 defense early in his career. The move paid off for Doleman, who recorded 21 sacks in the 1989 season, the highest total recorded that season and the third highest total ever. Doleman later played for the Atlanta Falcons and the San Francisco 49ers before returning to the Vikings for the 1999 season, his final season.