Peam, who joined the Habs as an assistant coach in July 2009, the month after head Coach Jacque Martin was hired, was cut loose following the team's sixth straight loss Monday, which dropped them to 1-5-2 to start the season.
Martin, who got the Canadiens into the playoffs the past two seasons after the team missed the playoffs the previous three years and is one of only nine NHL coaches with 600-plus victories, remains in his position.
"I want to thank Perry Pearn for his contribution to the Canadiens' organization over the past three years," General Manager Pierre Gauthier said. "He remains a very knowledgeable coach with a strong work ethic and is a true professional."
Gauthier added he has offered to allow Peam to remain with the organization in a different role.