He went for it as its British racing green bodywork was almost the same colour as his favourite football team, Celtic – although in later life he became a Rangers fan.
Now the CV8 he owned in the late 1960s is on sale for £135,000.
It even comes with its original logbook that lists the name of Sean Connery and his address at the time in Surrey.
At the time he bought the car in May 1967 – just after he finished acting in You Only Live Twice – the Bond star was among the highest-paid film actors in the world.
The two-door car has had a string of owners over the last 50 years and was acquired by the Jensen Museum in Church Stretton, Shropshire, four years ago.
They have listed it for sale to make more room in their collection.
Ulric Woodhams, of the Jensen Museum, said: “Only 500 CV8s were made and this is probably the most famous, given its connections.
“It seems Connery bought quite a few second-hand cars as they were better value, and he only ever bought green cars.
“We’re not sure why but my guess would be that at the time he was a big Celtic fan.”