Williams' numbers impressed the then-Phoenix Cardinals enough that they selected him in the third round of the 1991 NFL Draft, Williams quickly established himself with an exceptional rookie season, tying the NFC lead for interceptions. In 1994, he led the NFL in interceptions with 9. By 1997, Williams had already notched four Pro Bowl appearances and had established himself as the Cardinals' top cornerback, routinely covering the opponents' lead receivers. In the 1998 season, Williams helped the Cardinals win their first playoff game since 1947 by intercepting two passes from Troy Aikman in a 20–7 win over the Dallas Cowboys, and added another interception in the Cardinals 41–21 loss in the divisional round. Despite playing mostly for bad teams (1998 was the only time he played on a winning team during his 10 years in Arizona), Williams was recognized as one of the best cornerbacks in the league, making six Pro Bowls in all as a Cardinal. He is regarded as one of the best defenders and players in Cardinals history, as well as one of the greatest shutdown corners of all time. In 2000, he tied an NFL record, held by Jack Tatum of the Oakland Raiders, by returning a fumble (caused by Mark Maddox) 104 yards for a touchdown in a game against the Washington Redskins.