France, Italy and Spain have barred changes to EU working time rules because they set no date to end a UK opt-out from the 48-hour working week.
Workers in the EU put in an average of 40 hours per week
Ministers from the 25 EU countries were debating a proposal which would have cut the maximum hours people can work each week to 60, even after opting out.
It only contained vague words about ending the opt-out in future.
But the lack of a deal means that a bid to exclude doctors' "inactive" on-call time from working hours has collapsed.
The BBC's Tim Franks in Brussels says all EU member states are finding that a big burden.
For Britain's National Health Service, government officials put the cost at around £200m (300m euros) a year.
Employment Commissioner Vladimir Spidla said he would now start prosecuting countries that were in breach of the directive in its original form - because of their policies on doctors' on-call time, or for other reasons.
"We need to be logical... if a country does not respect the treaty we must bring proceedings against it," he said.
"We should move as fast as possible."
It is reported that only two member states are currently fully in compliance.
The UK, as the country which has fought hardest against the amended directive over the last two-and-a-half years, could be in the front line.
The European working time directive guarantees workers at least four weeks' paid annual leave, a minimum period of 11 hours' rest every 24 hours, at least one day's rest per week, and a rest break if the working day is longer than six hours.
It also says night workers should work a maximum of eight hours, on average, in every 24, and entitles them to health assessments.
The UK has fought moves to end the opt-out, on the grounds that labour market flexibility promotes economic growth and lowers unemployment.
Five countries, including France, Spain, Italy, Greece and Cyprus argue that the opt-out is bad for workers' health, and gives the UK a competitive advantage.
In the past, many more countries have lined up against the UK's opt-out.
But at the meeting on Tuesday, most accepted a compromise put forward by Finland, the current holder of the EU presidency, which would have preserved the opt-out while placing some new restrictions on its use.
The Finnish proposals would have cut the absolute maximum working week - for people using the opt-out - from 78 hours to 60.
They would also have scheduled a review of the opt-out, with a view to its "gradual ending" at a later date.
There were reports before the meeting that the UK might have been prepared to accept the Finnish proposal if the absolute maximum working week had been set at 65 or 70 hours, and if there had been legal safeguards to prevent courts overturning the opt-out.
Some professions, such as company executives and emergency workers, would still have been exempt.
Under the Finnish suggestion, a worker's 48-hour working week would have been averaged out over a reference period of up to 12 months, with the precise period being set by national governments.
This would have enabled most employers operating in markets where there are seasonal peaks to avoid violations.
The maximum working week of 60 hours, for those making use of the opt-out, would have been averaged over three months.