Manny Legace stopped Saku Koivu, Andrei Kostitsyn and Alex Kovalev in the shootout as St. Louis got its first road win in more than a month.
Boyes, who scored his team-high 38th goal in the second period, put a backhand past Jaroslav Halak on St. Louis' second attempt.
Keith Tkachuk scored on a two-man advantage in the first period for St. Louis, which got its first win seven games into a season-high nine-game road trip (1-5-1).
Andy McDonald also scored for the Blues, who had gone 0-7-3 on the road since a 4-1 win in Colorado on Feb. 14 to match the longest road losing streak in franchise history.
Mikhail Grabovski got Montreal even at 3 with his second goal of the season 6:36 into the third.
The sold-out crowd of 21,273 roared its approval as Grabovski beat Legace on a shot from the right side after receiving a pass from Sergei Kostitsyn.
Chris Higgins and Koivu also scored for the Canadiens, who are tied with New Jersey for the Eastern Conference lead with 90 points.
Montreal, which has eight games remaining, has a three-point lead in the Northeast Division over Ottawa, which has played one fewer game.
Halak lost for the first time in nine career starts at the Bell Centre. The 22-year-old Slovak stopped 25 shots as he started his second straight game after posting his first shutout of the season in Saturday's 3-0 win over the New York Islanders.
Tkachuk got his 22nd goal on a lengthy 5-on-3 early in the first period.
Montreal's Michael Ryder put the puck in the net 3:14 in but no goal was awarded because Koivu had already been called for interference.
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Tomas Plekanec was sent off 19 seconds later for holding Boyes and the Blues took advantage of the extra room on the power play as Tkachuk deflected Erik Johnson's shot from the left point past Halak to open the scoring 4:51 in.
Higgins drew Montreal even with his 22nd goal at 11:28, then assisted on Koivu's power-play goal 9:32 into the second that gave the Canadiens a short-lived 2-1 lead.
McDonald drew the Blues even 47 seconds later with his 15th goal at 10:19.
Paul Kariya got his second assist of the game at 15:57 when he set up Boyes, who was left alone in front of Halak to give St. Louis a 3-2 lead.
Notes: Kariya failed to score for a 17th straight game, dating back to the Blues' last road win. He has seven assists over that span. ... It was St. Louis' first game in Montreal since a 5-2 loss to the Canadiens on Jan. 13, 2004.
[Associated Press]
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