The 62-year-old was Ottawa Senators coach from 2011-15, going 114-90-35 and winning the Jack Adams Award voted as the top coach in the NHL in 2013. He won the Stanley Cup as an assistant with the Detroit Red Wings in 2008.
"Over nearly two decades as an NHL coach, Paul has filled every role on a coaching staff, winning a Stanley Cup and Jack Adams trophy along the way," Maple Leafs coach Sheldon Keefe said. "Adding someone of Paul's expertise and character to advise and assist our staff is something that we felt was very important as we seek to make tangible steps next season."
The Maple Leafs were eliminated by the Columbus Blue Jackets in Game 5 of their Stanley Cup Qualifier series after losing in the first round of the Stanley Cup Playoffs the prior three seasons.
MacLean was an assistant for the Anaheim Ducks (2002-04 and 2015-17) and Red Wings (2005-11). He made two other appearances in the Stanley Cup Final (Ducks, 2003; Red Wings, 2009).
Born in Grostenquin, France, MacLean scored 673 points (324 goals, 349 assists) in 11 NHL seasons as a forward with the St. Louis Blues, Winnipeg Jets and Red Wings, including three seasons with at least 40 goals; he scored an NHL career-high 41 goals with the Jets in 1984-85.
The Maple Leafs hired former NHL forward Manny Malhotra as an assistant on Sept. 17.