Yevgeny Plushenko, Sidney Crosby and Alexander Ovechkin bring their star powers to bear on the Winter Olympics on Thursday while veteran biathlete Ole Einar Bjoerndalen targets a record 13th medal.
Double Olympic gold medallist Plushenko, 31, is amongst the favourites as the men's figure skating short programme gets underway, but he faces competition from three-time world champion Patrick Chan, and Japan's Yuzuru Hanyu.
Plushenko is looking to become the most medalled man in Olympic figure skating history while Chan, 23, and Hanyu, 19, could become the first men from their countries to win the men's title.
Plushenko has been boosted by his solid skates on the way to team gold in Sochi and matching Gillis Grafstroem's record four medals between 1920 and 1932.
Chan has dominated the sport since finishing fifth at the Vancouver Olympics and has won the last three world titles, but Hanyu beat the Canadian in the Grand Prix final.
Other leading challengers will be Japanese Daisuke Takahashi, the Olympic bronze medallist, Tatsuki Machida and Spaniard Javier Fernandez, the world bronze medallist.
Sidney Crosby's defending ice hockey champions Canada start against Norway on Thursday while 2010 runners-up the United States begin by facing Slovakia.
Russia, led by Crosby's fellow NHL superstar Alexander Ovechkin, are under huge home pressure after their dismal showing in Vancouver four years ago where they beaten 7-3 by Canada in the quarter-finals.
The Russians eventually finished sixth in 2010 and are looking for their first Olympic title since the fall of the Soviet Union.
"When we lost to Canada it was a big failure for us," Ovechkin said. "I hope we will play in the finals. That is our main task, to fight for the gold."
In all six golds will be up for grabs Thursday with French biathlete Martin Fourcade looking for his second of the Games in the men's 20km individual, following his victory on Monday in the 12.5km pursuit.
The race could also see Ole Einar Bjoerndalen win a record 13th Winter Olympic medal after he just missed out in a fourth place finish in the pursuit.
He equalled his compatriot Bjorn Daehlie's record of 12 medals when he won gold in men's 10km sprint on Saturday.
In speedskating, US duo Heather Richardson, the winner of three World Cup races in four this season, and world record holder Brittany Bowe are favourites in the women's 1000m.
There should also be an all-American duel in the freestyle skiing with Nick Goepper and Gus Kenworthy easily the top contenders in the men's slopestyle.
In Nordic skiing, Poland's Justyna Kowalczyk tackles old rival Marit Bjoergen of Norway in the women's 10km classic.
Gold medals are also decided in the luge team relay and short track speed skating which debuts the women's 500m final.