He was drafted with the 10th overall pick in the 1993 NHL draft by the Quebec Nordiques. He played two seasons with the Nordiques and then one season with the Colorado Avalanche when the Nordiques moved to Colorado. In 1995, he was traded to the Montreal Canadiens with Martin Ručínský, and Andrei Kovalenko in exchange for Patrick Roy and Mike Keane. The trade was known as known in French as 'Le Trade' which was in reference to 1988's 'The Trade' of Wayne Gretzky. He played 4 seasons with the Canadiens and was traded to the Chicago Blackhawks on November 16, 1998. He played with the Blackhawks for 5 seasons and then was traded to the Pittsburgh Penguins for a fourth-round selection in 2006 draft on August 10, 2005. He injured his hip and lost twelve of thirteen starts. He was replaced as the starter by Marc-André Fleury in late November and was then put on waivers. The Buffalo Sabres signed Thibault as an unrestricted free agent on July 5, 2007 and he played as the backup to Ryan Miller for one season. He was not re-signed afted the season and retired from professional hockey in 2008.