The 45-year-old was stopped at 1:42 a.m. Friday on Interstate 264, police spokesman Jimmy Barnes said. Smith was charged with speeding, driving under the influence and refusal to take an alcohol breath test, Barnes said.
Smith was released on bond a few hours later.
Smith, who played for the Buffalo Bills and the Washington Redskins, is the NFL's all-time sacks leader. He was elected to the Pro Football Hall of Fame earlier this year.
Smith has two previous DUI arrests, but the first charge in 1997 was dismissed and he was acquitted in 2003.