Nakajima, who ended his frontline driving career after his World Endurance Championship campaign with Toyota last season, will take part in the historic event on the full 8.47-mile Circuit de la Sarthe on 30 June - 3 July at the wheel of a TOM'S 85C.
It is the same Toyota-powered chassis in which former Lotus and Tyrrell Formula 1 driver Satoru Nakajima finished in 12th place at Le Mans in 1985 together with Masanori Sekiya and Kaoru Hoshino.
Sekiya, who became the first Japanese driver to win Le Mans in 1995, will co-drive the privately-owned car together with 37-year-old Nakajima in the 60-minute Group C Racing event on the Saturday (2 July) of the historic event at Le Mans.
Nakajima, who now has a management role at Toyota Gazoo Racing Europe in Cologne, said: "It will be great honour to drive the 85C, which has a special place in the history of Toyota and also my family.
"I was born a few months before my father raced this car so I am too young to have seen it compete, but I have heard all about it.
"Group C was a legendary era for our sport and it has always been a dream of mine to drive a Group C car, so I would like to thank the owner, Mr Hisashi Kunie and Toyota Gazoo Racing for giving me this incredible opportunity.
"Although I know the Circuit de la Sarthe very well after 10 Le Mans, it will be a new adventure to discover the track in an old-school car like this so I am really looking forward to it."
The TOM'S 85C is a significant car in Toyota's Le Mans history.
A Group C project led by the TOM'S team and Japanese constructor Dome had kicked off in 1983; it was the dream of the respective bosses of the two companies, Nobuhide Tachi and Minoru Hayashi, to draw Toyota into the new prototype category.
The programme reached Le Mans in 1985 when each of their teams ran a solo 85C powered by a 2.1-litre turbo in-line four-cylinder Toyota engine.
The Japanese manufacturer provided increasing levels of technical assistance to the programme, which became a full-factory effort from 1987 at which point the cars became Toyotas for the first time.
The biennial Le Mans Classic is making a return to the historic racing schedule this season after an absence of four years as a result of COVID.
It will be the 10th running of the event established by Peter Auto boss Patrick Peter in 2002.