Rice started his senior season as a projected mid-first-round selection, but his stock rose due to his record-breaking performance in the NCAA Tournament, and he was selected #4 overall in the 1989 NBA draft by the Miami Heat.

In the 1994–95 season, Rice averaged 22.3 points a game (10th in the league) and made 185 three-point shots (6th in the league). Despite not being selected to play in the annual NBA All-Star Game, Rice participated in the NBA All-Star Long Distance Shootout at the 1995 All-Star game in Phoenix, and won the contest, edging out another sharp-shooter, Reggie Miller. Later during the season in a nationally televised game against Shaquille O'Neal and the Orlando Magic he scored a career-high 56 points on 20 of 27 shots from the floor including 7 three-pointers. The 56 points were an NBA season-high for the 1994–95 season. Despite his success, the Heat was unable to make the playoffs.

Charlotte Hornets

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Days before the start of the 1995–96 season, newly hired Coach/GM Pat Riley organized a trade in which Rice was sent to the Charlotte Hornets along with Matt Geiger in exchange for disgruntled Hornets center Alonzo Mourning who had refused any contract negotiations.

The Hornets paired Rice with high scoring forward Larry Johnson, and the two led the team to 41 wins. Rice led the team in scoring with 21.6 points a game and led his team in three-point field goals (171) and three-point shooting percentage (42%). He was also named to play in the 1996 NBA All-Star Game, but the Hornets failed to make the playoffs.

It would be the 1996–97 season in which Rice would earn the distinction of an elite player in the league. The Hornets had acquired veteran players Vlade Divac and Anthony Mason and no longer featured Johnson, and also hiring a new head coach and NBA legend Dave Cowens. Rice averaged 26.8 points a game during the season, placing him third in the league in scoring while leading the league in three-point shooting (47%) and minutes played. His play earned him his second straight All-Star Game election, and at the 1997 NBA All-Star Game set an individual All-Star game records of 20 points in the third quarter and 24 points in the second half to finish with 26 points for the game. He was then traded to the Lakers.

Before the 1999–2000 season the Lakers hired head coach Phil Jackson, who had won 6 NBA Championships with the Chicago Bulls teams that featured Michael Jordan and Scottie Pippen. The Lakers also acquired veterans such as Ron Harper, A.C. Green, as well as Rice's former Miami teammates John Salley and Brian Shaw. Led by the play of O'Neal, who won the MVP award for the season, and the all-star play of Bryant, the Lakers won 67 games for first place in the Western Conference. Rice started in 80 games and averaged 15.9 points as the team's third option with 84 three-point shots to lead the Lakers.

In the 2000 Playoffs, Rice averaged 12.4 points per game while shooting 41 percent from beyond the three-point arc, a career-best for the playoffs. The Lakers defeated the Sacramento Kings, Phoenix Suns, and Portland Trail Blazers in the first three rounds of the playoffs en route to advancing to the 2000 NBA Finals to play the Indiana Pacers. In the second game of the Finals, Bryant suffered an ankle injury, and Rice scored 21 points to help the Lakers take a 2–0 lead in the series. Rice would average 11.5 points a game for the series, including 16 points with 3 shots from three-point range in Game 6 as the Lakers defeated the Pacers 4 games to 2 to give Rice his first and only NBA championship.