Primeau was drafted third overall in the 1990 NHL Entry Draft by the Detroit Red Wings after playing two years with the Niagara Falls Thunder of the Ontario Hockey League. He split his first two professional seasons with Detroit and their then-American Hockey League affiliate, the Adirondack Red Wings. He set career highs in assists, points and plus/minus in 1993–94. He made his only Stanley Cup Finals appearance while with the Red Wings in 1995, losing in a sweep to the New Jersey Devils. Primeau held out after the club signed Igor Larionov and after playing for Canada in the 1996 World Cup of Hockey, Detroit traded him to the Hartford Whalers in exchange for Brendan Shanahan and Brian Glynn a few days following the start of the 1996–97 season. Primeau became a leader with his new team when the franchise moved to North Carolina and became the Carolina Hurricanes, being named team captain in 1998–99. However, he missed the majority of the 1999–2000 NHL season after holding out and was traded to the Philadelphia Flyers in exchange for Rod Brind'Amour, Jean-Marc Pelletier and a 2000 second-round draft pick on January 23, 2000. On May 5, 2000, Primeau scored the game-winning goal in the longest game in modern NHL playoff history against Ron Tugnutt of the Pittsburgh Penguins in Game 4 of the Eastern Conference Semifinals. Only two games, in 1933 and 1936, were longer. In his first full season with the Flyers, Primeau led the team in goals and tied his career-high in points. Early in the following season, he was named team captain after defenceman Éric Desjardins resigned from the position. After posting nearly identical seasons statistically in 2001–02 and 2002–03, Primeau was given the task of centering a more defense-oriented line in 2003–04. He did well enough to earn a place in the 2004 NHL All-Star Game, the second of his career. In the 2004 Stanley Cup playoffs, Primeau recorded nine goals and seven assists for a total of 16 points; it was the best playoff year of Primeau's career and his play carried the team to within a game of the Stanley Cup finals. In Game 6 of the Eastern Conference finals, against the Tampa Bay Lightning, Primeau scored the game-tying goal with 1:49 left in regulation. The Flyers won the game, 5–4 in overtime, sending the series back to Tampa for Game 7. The Flyers went on to lose that game by a score of 2–1. Hockey legend Phil Esposito later told Primeau that, "During the '04 playoffs, when you and the Flyers took the Lightning to seven games, you were the most dominating player I ever saw. More than Orr, Howe, Gretzky, or anyone." Nine games into the 2005–06 season, Primeau suffered a concussion which ended his season. As a result of ongoing post-concussion syndrome, he officially announced his retirement on September 14, 2006. On February 12, 2007, the Flyers honoured Primeau before a game against the Detroit Red Wings, the team which originally drafted him. An emotional Primeau thanked the fans for welcoming him back. Primeau has been a resident of Voorhees Township, New Jersey.