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Bradley Wiggins is seeking to become the first man to win the Tour de France and Olympic gold in the same year on Wednesday.
The 32-year-old last month became the Tour's first British winner and was aiming to carry his form into the 44-kilometre Olympic time-trial at Hampton Court.
Any medal for three-time Olympic track champion Wiggins would take his tally to seven in his fourth Games, surpassing rower Sir Steve Redgrave's British record haul.
"The Tour is such a good boot camp for this," said Wiggins, who competed in support of Mark Cavendish in the 250km day one road race.
"We handled that pretty well, so an hour time-trial to make history should be a doddle."
Wiggins won the two long time-trials at the Tour by convincing margins, the second 53.5km test to Chartres effectively sealing his yellow jersey.
The 32-year-old Londoner believes that was the best time-trial of his career.
"The benchmark is there from Chartres," added Wiggins, who was runner-up at last September's World Championships.
"Nothing is going to change from that performance. I have 100% faith in the training Tim (Kerrison, the Team Sky coach) has set me.
"I've done enough now to realise that it is not all suddenly going to collapse. My performances have been so consistent all year and I've no reason to think that is going to change."
Chris Froome was Wiggins' closest challenger during the Tour and the duo are seeking to win Britain's first Olympic road medals since Atlanta, when Chris Boardman won time-trial bronze and Max Sciandri was third in the road race.
Germany's Tony Martin, the world time-trial champion, defending Olympic champion Fabian Cancellara of Switzerland, Australia's Michael Rogers and Taylor Phinney of the United States are all likely to be in medal contention.
Emma Pooley is seeking a medal in the 29km women's time-trial, despite the flat course being far from ideal for a rider who favours undulating terrain.
Pooley, who won silver in Beijing, the 2010 world championship and took bronze last year, said: "Ever since Beijing the time-trial has been my thing.
"I was really pleased last year at the World Championships, because it was a flat course and I surprised myself by doing better than I expected.
"I've trained for that kind of course and I'll do my best. That's all you can do in a time-trial."
Lizzie Armitstead, who won Britain's opening medal of the Games in Sunday's road race, is also set to be in action.
She said: "I'm looking forward to riding an event without any pressure and enjoying being pushed round by the crowd."