The #8 Peugeot will take a comfortable lead into the final quarter of the Petit Le Mans after the #1 Audi crashed in traffic during a huge battle between them.
The two cars had worked their way back into first and second following earlier delays, with Peugeot's Franck Montagny and Audi's Romain Dumas then commencing a spectacular battle - which sometimes saw light contact between them - as the race headed into sunset.
But it came to an abrupt end on lap 296, when Dumas clipped a GTC Porsche while trying to follow Montagny through a gap, and speared into the wall after Turn 7. He was unhurt.
The crash ends Audi's hopes of victory as the #2 car had already been delayed in several early incidents and is down in 34th.
The ORECA Peugeot will rise to second after Dumas' shunt, but is three laps behind the race-leading factory car.
Aston Martin Racing's Lola comes next, ahead of the two LMP1 Oak Pescarolos and the Rebellion Lola-Toyota.
The GT battle has been as tight as the overall lead fight, with nothing to choose between current leader Gianmaria Bruni's AF Corse Ferrari and the BMW of Joey Hand.