Thibault declined to accept a demotion to AHL Wilkes-Barre/Scranton on Monday when the team asked him to go down and work on his game. If he clears waivers and refuses the assignment again, the Penguins could suspend and stop paying him.
Thibault, expected to be the starter when the season began, is 1-7-2 with a 4.38 goals-against average and an .880 save percentage in 12 games.
The Penguins made the move one day after calling up goaltender Marc-Andre Fleury from Wilkes-Barre/Scranton. Fleury was the top pick in the 2003 NHL draft.
Thibault signed a $3 million, two-year contract after being traded to Pittsburgh by the Chicago Blackhawks in August.