Rossi will drive a BMW M4 GT3 prepared by Team WRT in the second round of the Le Mans Cup, which forms part of the Road to Le Mans support package.
This would be Rossi's first taste of the Circuit de la Sarthe, although he has previously driven on the Bugatti layout that is an annual fixture on the MotoGP calendar.
His team-mate for the two 55-minute races that will take place on Thursday and Friday ahead of the centenary edition of the French endurance classic is yet to be revealed.
The announcement follows Rossi becoming a full-fledged BMW factory driver this year and revealing aspirations to go for outright honours at Le Mans in a Hypercar.
The Italian is due to test the BMW M Hybrid car at some point before the end of the year ahead of the German manufacturer expanding its LMDh programme beyond the IMSA SportsCar Championship and into the World Endurance Championship in 2024.
The BMW M4 he will race at the Circuit de la Sarthe on June 8 and 9 will also become eligible to race at Le Mans next year following WEC's decision to adopt GT3 regulations to replace the outgoing GTE class.
In a recent interview with Motorsport.com, Rossi reiterated his desire to tackle the twice round-the-clock enduro, potentially in the top category.
“I want to participate in the 24 Hours of Le Mans,” he said. “Now I am racing GT cars, but there would also be the possibility of competing there with Hypercar.”
Rossi is currently competing in his second full-year of car racing - and first with BMW - with his 2023 programme primarily focused on the GT World Challenge Europe with WRT.
This year’s Le Mans Cup grid will comprise several familiar names, most notably ex-Corvette ace Jan Magnussen.
The father of Haas Formula 1 driver Kevin Magnussen will pull double duty during the week as he is also due to race for the Inter Europol team in the LMP2 Pro/Am division of the 24-hour classic.
Aston Martin, Honda, Porsche, Audi, BMW, Ferrari, Mercedes and Lamborghini will all be represented in the Le Mans Cup.
Frederic Lequien, CEO of Le Mans Endurance Management said: "Once again the Road to Le Mans has attracted a large entry with star names running alongside the series regulars and to have Valentino Rossi on the grid is a massive boost for the event.
“It also demonstrates the importance of the Michelin Le Mans Cup in endurance racing. I would like to wish everyone taking part in the 2023 Road to Le Mans the very best of luck in this very special anniversary year for Le Mans."
