Donna Smith, 27, and her 25-year-old partner Matthew Hughes were reported missing by their relatives and were last seen getting into the car at home in West Drayton, west London, at about 5.30pm.
The Metropolitan Police believe the couple were heading out of London.
After the report was filed, cops were informed the pair's blue Vauxhall was involved in a crash with a parked car in the Ruislip area.
But the couple were nowhere to be found when officers arrived at the scene.
Scotland Yard said: "Officers are growing increasingly concerned for their welfare and are appealing for anyone who knows of their whereabouts to get in contact with police."
Miss Smith is described as a white female of slim build.
She is 5ft 7ins with light brown hair and was last seen wearing a black coat and jeans.
Mr Hughes is a white male with dark brown hair and of a skinny build.
He is 5ft 11ins and has an Ave Maria tattoo on his forearm.
Hughes was last seen wearing a black coat and jeans.
More to follow…
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