Britain's Nicole Cooke's bid for gold in the women's road race was scuppered by Sara Carrigan.
The Australian broke clear in the dying minutes to take gold ahead of Germany's Judith Arndt, while Cooke had to make do with fifth place.
Cooke had been in contention for a medal but clipped a barrier in the latter stages.
Despite catching the group going for bronze, she failed to outpace her rivals on the line.
Cooke had been favourite for victory in the race and her cause was helped when Leontien Zijlaard van Moorsel crashed out in dramatic fashion.
Earlier Spain's Eneritz Iturriaga Mazaga and Sonia Huguet of France opened up leads of more than a minute on laps five and six respectively.
Lyne Bessette was the next rider to jump off the front, and shortly after being reeled back into the main group she was involved in the crash that could rule Van Moorsel out of the time-trial.
When Cooke found herself stranded in a secondary group when six riders burst off the peloton to close down Huguet, she showed her strength in bridging the gap.
But on the final lap of the race she failed to get with the break of Arndt and Carrigan.
Her hopes of a medal were effectively dashed when she made slight contact with a barrier and used her final efforts trying to catch the bronze-medal group.
The day before the race, her father and coach, Anthony, was quizzed by police after daubing his daughter's name on the route.
He was spotted by a patrol and taken to a local police station before being released without arrest, the Greek Ministry of Public Order said.