Brandon Prust, who left the game late in the first period with an apparent shoulder injury, returned to score a goal and set up one by Travis Moen for Montreal (38-25-7), which won its third game in a row. Vanek got his first goal in six games since he was acquired in an NHL trade deadline deal.
Rookie Nathan MacKinnon scored a highlight-reel goal and Max Talbot and Jamie McGinn also scored for the Avalanche (44-20-5), which lost for only the third time in 10 games. The Avs end a three-game road trip Wednesday night in Winnipeg.
Some wondered how the Bell Centre crowd would react to Roy, who won Stanley Cups for the Canadiens in 1986 and 1993 but later demanded a trade and was on the outs with the organization until 2008 when they retired his No. 33 jersey.
It was clear that all was forgiven when the former goaltender got his first long ovation when he was shown on the scoreboard during the national anthems.
Roy's team responded with a strong opening period.
No. 1 overall draft pick MacKinnon put on a show as he ragged the puck in the Montreal zone for most of an entire shift. Then he got the puck alone in front of the net off a strange deflection and deked Carey Price for his 23rd goal of the season at 18:03.
Talbot was parked at the doorstep to knock in a Matt Duchene feed at 9:33, but Moen tied the score at 10:21 with his second of the year and his first since Nov. 22. Prust dove to chip the puck into the middle, where Moen caught it, then did a spin-around move to beat Giguere with a backhand.
Giguere took a holding the stick penalty and Vanek made him pay as he converted a Max Pacioretty feed on a power play for the game-winner at 14:45. Montreal was on the power play again when Vanek deflected an Alexei Emelin shot in at 17:40.
Notes: It was Roy's first game against Montreal since he was a player on Nov. 6, 2001. Roy opted to put Montreal native Giguere in goal over No. 1 Semyon Varlamov. . .Paul Stastny returned from after missing four games with a back injury. . . The Avs went into the game with the NHL's fourth best power play and Montreal with the fourth best penalty kill.
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