Buckley was a two-year starter and three-year letterman at Florida State (1989–91), and left as the school's all-time leader in interceptions (21) and interception return yards (501). His career interception yardage total of 501 is an NCAA record also tied school records for touchdowns off interception returns (four) and punt returns (three). He was named first-team All-American and won Jim Thorpe Award, given annually to nation's top cornerback, as a junior. He led the nation with 12 interceptions for 238 yards and two touchdowns. He was named second-team All-American by Associated Press, The Sporting News and The Football News as a junior. Had six interceptions with two returned for touchdowns. He finished 7th in the Heisman voting in 1991. He played two years of varsity baseball and was a sprinter on the outdoor track team for one year. He was drafted by the Green Bay Packers in the NFL draft.
Buckley is the only player with 50+ interceptions to never make a pro bowl. In a game against Cincinnati in 1992, his rookie season, Buckley set what remains a current record as the youngest player to return a punt for a touchdown in NFL history (7008671781600000000♠21 years, 105 days). That was his only punt return for a touchdown of his career. In 1996, he led the league in interception return yards with 164.
He had at least one interception in 13 consecutive seasons. In the 2001 AFC Championship game against the Pittsburgh Steelers, Buckley had an intereception in the 24-17 win. He earned a Super Bowl ring 2 weeks later in the win over the St. Louis Rams.
Finally getting his first on the field coaching position, Buckley was hired by his collegiate head coach's son, Terry Bowden, at the University of Akron in January 2012 to coach cornerbacks. This reunited him with Coach Chuck Amato and with Coach Todd Stroud—who he played for, and coached with at FSU.