Organisers said doctors had submitted a report to the marshals "disallowing him from racing after the accident he experienced."
Duval won the race last year, as well as the world endurance championship, in a car he shared with Denmark's nine times winner Tom Kristensen and now-retired Scot Allan McNish.
Kristensen is seeking a record-extending 10th win this year with Lucas Di Grassi replacing McNish and hoping to become Brazil's first winner.
The race at the Sarthe circuit in western France starts on Saturday.
(Reporting by Alan Baldwin, editing by Sudipto Ganguly)
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