The US coffee chain has signed an initial one-year deal with Guardian News and Media to run from November 5.
The chain decided to end its deal with The Times and Sunday Times after a business review earlier this year, which established Guardian News and Media would be a "better partner", according to a Starbucks spokeswoman.
Starbucks and Times Media agreed their pioneering deal in March 2004, establishing a new sales channel for The Times and Sunday Times.
Brian Waring, marketing director of Starbucks UK, said: "We hope that the two million people who walk through our doors every week will enjoy being able to buy a copy of The Guardian along with the favourite cup of coffee."
The Times was unavailable for comment at the time of publication. It recently invested in a free home delivery service for readers within the M25.
Starbucks was recently carpeted by for wasting millions of litres of water each day after a special investigation by the red-top, which was followed up by .
The chain subsequently pledged to reverse its policy of leaving the cold tap on its 'dipper well' sinks on all day to rinse utensils.