With Tom Gilbert in the box serving an interference penalty the Sedin twins went to work and the end result was a beautiful deke by Daniel Sedin for the overtime winner.
Montreal managed to salvage a point in the loss despite trailing 2-0 early in the third.
Alex Galchenyuk cut the Canucks lead to 2-1 at 12:11 of the third. Then at 17:27 of the final frame, Max Pacioretty ensured the visitors would get at least a point tying it 2-2.
Nick Bonino and Brad Richardson scored the other Vancouver goals.
Vancouver is now an impressive 7-3-0 to start the season and sit in second place in a tough Pacific Division.