Thicke, 36, met Patton, 38, when he was just 14, and they married in 2005. Their teenage romance was chronicled in 'For the Rest of My Life' a single from his 2013 album 'Blurred Lines', reported People magazine.
"We will always love each other and be best friends, however, we have mutually decided to separate at this time," read their joint statement.
They were most recently spotted together at the Grammys but tabloids have been abuzz with rumours that they were headed for a split since Thicke's raunchy performance with Miley Cyrus at the VMAs in August.
Thicke was also hit with rumours that he cheated on Patton during an August 25 party.
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