Doleman attended William Penn High School in York, Pennsylvania, and graduated in 1980. He spent a postgrad year at Valley Forge Military Academy in 1981.
Doleman played football collegiately at the University of Pittsburgh. He was a star linebacker and defensive end for the Pitt Panthers from 1981 to 1984. He ended his career at Pitt with 25 sacks which was good for third all-time at the time of his departure. That total still ranks sixth in Pitt annals.
Doleman was selected by the Minnesota Vikings in the 1st round (4th overall) of the 1985 NFL Draft. He 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 fourth highest total ever. The 21 sacks in a single season was a Vikings record until Jared Allen recorded 22 sacks in 2011. Doleman later played for the Atlanta Falcons and the San Francisco 49ers before returning to the Vikings in 1999 for his final season.