Britain's Bradley Wiggins took silver but German rival Tony Martin proved a class above the field to lift his first time trial world title in Copenhagen.
Pre-race favourite Martin lived up to his billing, covering the 46.3km course in 53 minutes 43.85 seconds.
Wiggins finished one minute 15.83 secs back then saw defending champion Fabian Cancellara slip on a corner.
"This is what it was all about: come here, get a medal and finish off a great year," Wiggins told BBC Sport.
"It was a real honour to be out there with those two guys [Martin and Cancellara], who are probably the best two time-trialists in the world.
"I feel sorry for Fabian in a way - he's dominated this event the last few years - and Tony's worked hard to get up there close to him. He's finally cracked it and won by a significant margin.
"I've been there or thereabouts in time trials all year and we've probably been the most consistent three time trialists. It's good to finish off with a medal, up there with those two."
Cancellara was 4.76 secs off Wiggins while GB team-mate David Millar, last year's silver medallist, trailed Martin by two minutes and 45 seconds to place seventh.
Millar never threatened the podium and found himself quickly swept up by the phenomenal Martin, twice a bronze medallist in the previous two years.
"It's amazing for me. David Millar was one of the favourites and when you pass him, you must have had a good ride," said Martin.
"That gave me a lot of motivation and morale, it was really helpful.
"For me [being the favourite] was positive pressure. I've learnt to work with it."
Wiggins has endured a rollercoaster year, winning the Tour de France warm-up the Criterium du Dauphine, breaking his collarbone during the Tour itself but recovering to finish third overall in the Tour of Spain, the Vuelta a Espana.
"I was lying in hospital [having withdrawn from the Tour] and I wanted something to target for the rest of the year," he said after the race.
"I decided to try to do a good Vuelta time trial and we did the Vuelta as preparation for this. This has topped it off."
As Wiggins looked for the perfect finish to the season, it soon became clear he would not match Martin.
Once he crossed the line ahead of Germany's Bert Grabsch, bronze looked assured and the question of silver came down to the stamina of a struggling Cancellara.
Olympic time trial champion Cancellara, who won each of the four World Championships trials he entered between 2006 and 2010, saw his advantage over Wiggins crumble in patchy, light rain around the Danish circuit.
He lost his grip coming into a corner near the home straight and ended up narrowly behind the Briton.
Wiggins, who has won three Olympic and six world titles on the track, added: "After all the track medals and Olympic medals, it's nice to come to the Road Worlds and get a medal.
"To be up there with those two guys completes my transition to a road rider from track."
Wiggins and Millar will next appear in Britain's powerful seven-man lead-out train for Mark Cavendish in Sunday's road race.
Sprinter Cavendish believes he will never have a better opportunity to become the world champion than on the flat Copenhagen course - which invites a bunch sprint finish - helped by a team others have hailed as the strongest British line-up in history.