Canada and South Korea played in the Page 1-2 playoff game. South Korea will now face Sweden in the semifinal.
Rocque, of Edmonton, finished tied with South Korea atop the overall standings with identical 7-2 records. But the Koreans earned first after beating Canada 8-6 during the round robin.
"It's amazing. It's unexplainable right now, it's so exciting," said Rocque following her win. "We really just wanted to come here and hopefully medal.
"Now that we're guaranteed one, we are so excited. Hopefully the gold but we'll be happy either way. I blinked and that game was over. It was a really fast-paced game with a lot of good shotmaking. It was an exciting game to play in."
Canada led 5-4 after eight ends but got into trouble in the ninth when Rocque slid wide on a draw that allowed South Korea to steal two.
But in the 10th end, Rocque faced a draw for two and the win and this time made the shot.
"I'm just so proud of the girls, they've played so well," Rocque said. "We wanted this so badly, it's awesome and we're glad all the hard work is finally paying off."
Winnipeg's Braden Calvert takes on Switzerland in the men's Page 3 versus 4 contest Tuesday. The Canadians finished third with a 6-3 record.