The new policy means that drivers must take an uninterrupted six-hour break after 10 hours, and will not be able to log on to the app during that time.
The company had already been messaging drivers who were working too long to switch off its app.
"We believe this is an industry first and are not aware of any other private hire operator in the UK that has introduced such a limit," Uber said in a statement.
Uber is currently appealing against the withdrawal of its licence in London over the way in which the company reports serious criminal offences and obtains criminal record checks for its drivers.
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Uber is also appealing against an employment court ruling that would give its drivers the right to paid holidays and the national minimum wage.
Uber has around 40,000 drivers in London and 50,000 in Britain as a whole.
"We received evidence of Uber drivers being logged into the Uber app for more than 60 hours per week so we welcome the introduction of limits to driver hours.
"We look forward to seeing how this will work in practice and hope other companies will quickly follow suit," she said.
But James Farrar, head of the Independent Workers Union of Great Britain, said drivers were tired "because they are not earning enough".
"If Uber forces drivers to work less without paying more it is just going to depress hourly earnings even further below the minimum wage and push drivers to the brink," he said.
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