Daniel Sedin, Zack Kassian, Chris Higgins and Dan Hamhuis scored for the Canucks (10-5-1), who rebounded from a disappointing 2-1 loss to the Detroit Red Wings on Wednesday with one of their best efforts of the season.
Henrik Sedin, who along with his brother signed a four-year contract extension worth US$28 million on Friday, picked up an assist on Daniel's first-period goal to extend his point streak to 11 games (three goals, 10 assists).
James Reimer kept the Maple Leafs (10-5-0) in it most of the night, making 43 saves in defeat as Toronto was outshot for the 13th time in 15 games this season.
The Maple Leafs also saw their three-game winning streak come to an end.
Prior to the opening faceoff, the Canucks retired Pavel Bure's No. 10 in a ceremony that lasted 20 minutes that included a number of standing ovations. Dubbed the "Russian Rocket" for his blazing speed, Bure scored 254 goals and 224 assists in 428 games with Vancouver over seven seasons.
Leading 1-0 after a raucous first period, Vancouver made it 3-0 with goals in quick succession early in the second.
Kassian made it 2-0 by firing a shot past Reimer that deflected in off Toronto defenceman Cody Franson at 2:07 on a play that might have cost the Maple Leafs more than a goal against. Gritty forward Dave Bolland suffered a laceration to his left leg on a hit by Kassian moments before the goal and had to be helped to the locker-room. He did not return.
Higgins then ripped a shot past Reimer on a 2-on-1 rush to make it 3-0 at 5:05 after rookie Maple Leafs defenceman Morgan Rielly misplayed the puck at the Vancouver blue-line.
After Toronto killed off a two-minute two-man advantage, Maple Leafs forward James van Riemsdyk was stoned by Luongo on a backhand chance on a power play late in the period that would have given his team life after 40 minutes.
Toronto was shorthanded three times in the first nine minutes of the third period, but Reimer kept his team alive before Hamhuis rounded out the scoring at 14:48.
The Canucks came out with speed and passion that would have made Bure proud in the first period, taking a 1-0 lead on the scoreboard and an 11-0 edge on the shot clock before the game was 10 minutes old.
Reimer was strong early with four big stops during a frenetic sequence just over four minutes in, including one on Mike Santorelli on a 2-on-1 break and a miraculous desperation pad save on Alexandre Burrows that could be an early-season candidate for save of the year.
Vancouver finally got one past the Toronto goalie at 5:55 on the power play. The Canucks came into the game ranked tied for 28th in the NHL with the man advantage but connected with Nazem Kadri off for hooking when Ryan Kesler's touch pass found Henrik Sedin in front. The Canucks captain rifled a shot that went off Daniel Sedin for a goal that was just Vancouver's fifth on power play all season.
Toronto got its first shot of the night at 8:17, but Phil Kessel's shot from the slot was gobbled up by Luongo.
The Maple Leafs sniper was in the middle of the action again with five minutes to go in the period when he dropped the gloves with Burrows in a fight that saw both players tumble to the ice almost immediately.
Maple Leafs tough guy Frazer McLaren then drew a crowd with a few minutes to go when he bumped Luongo, knocking the goaltender's mask off.
Notes: Luongo's other shutout this season came against the Buffalo Sabres on Oct. 17. ... Daniel Sedin's goal in the first period was just the Canucks' second power-play goal at home this season. ... Saturday's game marked the return of Mason Raymond to Vancouver. The Maple Leafs forward, who spent seven seasons with the Canucks, was not offered a contract in the off-season and made the Toronto roster on a tryout. So far in 2013-14, the 28-year-old has five goals and six assists. ... Former Canucks tough guy Gino Odjick got a big ovation during Bure's ceremony. Also on hand was Pat Quinn, who was Bure's first coach with Vancouver.