Multi-millionaire Christopher Cox was driving the Ferrari 250 GTO with his wife Ann, who is understood to have suffered a broken leg in the accident in Central France.
Cox was taking part in the 50th anniversary tour of the Ferrari 250 GTO - an Italian sports car dubbed as the 'Picasso of the motoring world.'
The Ferrari, which is one of only 39 ever built, values more than 20 million pounds, the Daily Mail reported.
The incident took place outside Saint-Etienne-des Guirets, near Blois when the enthusiasts drove the iconic Gueux racing circuit in Reims before visiting the Abbey of Hautvillers as part of the five-day tour
Pink Floyd drummer Nick Mason and JCB boss Sir Anthony Bamford were two of 21 groups of multi-millionaire Ferrari fans taking part in the 50th anniversary jaunt.
Ferrari built the 250 GTO between 1962 and 1964 with the 174 mph sports car sold with a 6,000 pounds price-tag.
The value of the 250 GTO has skyrocketed in recent years with one green model built for Stirling Moss selling last month for a world record 22.7 million pounds.
The model involved in Friday's crash was built in April 1962 with the chassis number 3445GT.
The car was resprayed blue from initial red colour, with a yellow central stripe in 1963 to match the colours of Sweden after race driver Ulf Norinder's nationality.
The high value car was later rebodied, but in 1976 was crashed and underwent a full restoration before Mr Cox bought the vehicle in 2005.
US actor Chris Evans is also understood to have recently sold his 18 million pounds model of the Ferrari.
The 250 GTO uses a 3-litre V12 engine developing 300 bhp which results in a 0-60mph time of 6.1 seconds and a top speed of 174mph.
