Caroline Ouellette scored her second goal of the game 1:50 into overtime to give Canada a 5-4 win over the U.S. on Saturday.
Canada may have won Olympic gold in 2010, but it was the country's first world title since 2007 in Winnipeg.
The U.S. beat them in three straight finals after that, including an overtime victory last year in Switzerland.
"We were really sick of silver and I think we cannot say anymore they're better than them," Ouellette said. "They have an amazing team and it's who is going to be better on any given day.
"Tonight, we wanted to make sure that it was us."
A bad line change by the U.S. gave Canada an odd-man rush to the net. Ouellette took a pass from Meghan Agosta and fired a shot past U.S. goaltender Molly Schaus to close the latest chapter of the long history between the North American rivals.
"Really who made the play of the game on that was Tessa Bonhomme," Ouellette said. "She saw I was coming off the bench, she went to the net and brought everyone with her. I yelled as loud as I could.
"I think Meghan Agosta was about to shoot and she heard me. She passed to me and Tessa Bonhomme was in front of the goalie and she didn't see anything. I just had to shoot."
Canadian captain Hayley Wickenheiser scored short-handed in the first period. Assistant captains Ouellette and Jayna Hefford also scored. Those three forwards are the longest-serving players in Canada's current lineup.
Two-time Olympian Agosta scored a power play goal late in the third period to send it into extra time. She also had a pair of assists.
"The veterans players, we stepped up and led the way," Wickenheiser said. "We've been in these battles a long time and it was weighing on us, the losses from the years previous and none of us wanted to see that happen again."
Goaltender Shannon Szabados made 40 saves in the victory.
The Americans fought back from a 3-1 deficit in the second period with three unanswered power-play goals.
Defenceman Gigi Marvin scored twice, with Kendall Coyne and Brianna Decker adding goals for the hosts. Schaus stopped 34 of 39 shots for the victory.
Wickenheiser and rookie defenceman Laura Fortino were named to the tournament all-star team.
The U.S. and Canada have met in the final of all 14 world championship starting with the first one in Ottawa in 1990.
Canada took its worst beating ever from the U.S. in a 9-2 loss to open the tournament. The Americans scored five goals in the first five minutes and 32 seconds and so thoroughly dominated Canada that the U.S. seemed the clear favourite here.
The visitors were ready to match their pace in the final, however. They blocked shots and kept the U.S. from getting to the rebounds they'd turned into goals in the first game. The Canadians also did a better of slowing the Americans down through the neutral zone to blunt their attack.
It was quickly apparent this was going to be another in a long line of fast, hard and mean games between the North American women, to the delight of the 4,000 filling the University of Vermont's Gutterson Fieldhouse. The Fighting Catamount band provided a college football feel.
Canada's slogan coming into this world championship was "skill and sandpaper." There was too much of the latter late in the second period and to start the third as the U.S. made good on three straight power plays to take the lead.
Marvin's shot from the blue-line deflected off the post and in at 2:57 of the third period to put the U.S. in front 4-3. She had tied the game at 18:16 of the second period, while Decker scored at 16:43.
But it was the U.S. in penalty trouble late in regulation, allowing Agosta to tie the game with a power-play goal at 17:22.
Ouellette made it 3-1 for Canada putting her own rebound past Schaus at 5:36 of the second period. Canada swarmed the net with Hefford banging in a rebound for a power-play goal at 4:07.
Coyne tied the game at 12:54 of the first period off a quick cycle in the offensive zone. The U.S. got bodies in front of Szabados and Coyne scored on a deflection.
Wickenheiser forced a turnover in the neutral zone for a breakaway on Schaus. She knocked in her own rebound for a short-handed goal at 7:37.
"We said in the room this was our movie to make this year and that we should just got for it and play free to win instead of fearful to lose," she said. "That was the attitude I think we had. Bonhomme jumps up into the rush and takes a chance and that's how you score.
"Safe is death and we didn't play safe."
With six players appearing in their first world championship, Canadian head coach Dan Church shortened his bench. Bonhomme actually didn't play that much during the game, but played a pivotal role in the end.
"Across the board, everybody who played in the game tonight and the players who didn't play in the game tonight, who saw limited action, they all played a really important role in our success this week," he said.
There was sandpaper on both sides of the puck. Forearms and sticks clashed when the whistle blew around the net.
Canada's Marie-Philip Poulin and U.S. counterpart Jocelyne Lamoureux got into it more than once in the first period. Jennifer Wakefield and American defender Kacey Bellamy exchanged a punches in the second and were both send to the penalty box.
Switzerland beat Finland 6-2 for the bronze medal, which was the first medal at the women's world championship for the Swiss.
Sweden, Russia and Germany finished fifth to seventh. Slovakia was relegated to the second-tier world championship.
The 2013 women's world championship will be held in Ottawa.
Notes: Total attendance at the tournament was 26,205 for an average of 1,247 per game . . . Swiss goaltender Florence Schelling, U.S. defender Gigi Marvin and American forwards Monique-Lamoureux Kolls and Kelli Stack joined the Canadians on the all-star team . . . Schelling, Stack and Finland defender Jenni Hiirikoski were chosen the top players at their positions by the IIHF.