Hunley was born in Petersburg, Virginia, and graduated from Petersburg High School.
Hunley attended the University of Arizona, where he played for the Arizona Wildcats football team from 1980 to 1983. As a junior in 1982 and again as a senior in 1983, he was recognized as a consensus first-team All-American—and became the first Arizona Wildcat football player to receive consensus All-American honors.
He started his NFL coaching career through the NFL Minority Fellowship Coaching Program in 2002 as the defensive line coach for the Washington Redskins under Steve Spurrier, where he met Marvin Lewis. He then moved to Linebackers coach under Lewis for the Cincinnati Bengals from 2003 to 2007; he was fired after a disappointing season and a flurry of player injuries and suspensions. He also served on the board of directors for the Black Coaches Association.
Hunley and his wife Camille, have two daughters, Alexis and Kenady. His younger brother, Lamonte, was also an All-American linebacker at Arizona. He founded the Ricky Hunley Football Camp, a non-profit instruction center for high school boys.