In the process, Rossi turned a best lap of 1m 33.408s which was 0.27 seconds under the lap record he set on the 990cc Yamaha YZR-M1 on the final lap (lap 28) of the 2005 race.
Rossi's pole time for Sunday's race was also under his 800cc MotoGP class lap record of 1m 34.215s, set in 2008.
Fiat Yamaha team-mate Jorge Lorenzo, winner of the Spanish GP at Jerez was just a fraction of a second slower on his best lap than Rossi, with a 1m 33.462s effort, beating out Repsol Honda's Dani Pedrosa, who rounded ou the front row of the grid with a 1m 33.573s effort.
It was the seventh time that Yamaha team-mates Rossi and Lorenzo have qualified 1-2 in a MotoGP event.
Heading the second row of the grid was Marlboro Ducati's 2007 MotoGP World Champion Casey Stoner (1m 33.824s) with team-mate Nicky Hayden alongside him with a 1m 33.84s effort.
Local heart-throb Randy DePunet gave the French fans something to skite about, rounding out the front row on his satellite Honda with a 1m 34.074s effort.
The qualifying times were:
1 Valentino Rossi Yamaha ITA 1'33.408
2 Jorge Lorenzo Yamaha ESP 1'33.462
3 Daniel Pedrosa Honda ESP 1'33.573
4 Casey Stoner Ducati AUS 1'33.824
5 Nicky Hayden Ducati USA 1'33.845
6 Randy De Puniet Honda FRA 1'34.074
7 Andrea Dovizioso Honda ITA 1'34.204
8 Colin Edwards Yamaha USA 1'34.304
9 Loris Capirossi Suzuki ITA 1'34.306
10 Aleix Espargaro Ducati ESP 1'34.514
11 Marco Melandri Honda ITA 1'34.523
12 Ben Spies Yamaha USA 1'34.920
13 Marco Simoncelli Honda ITA 1'34.942
14 Hiroshi Aoyama Honda JPN 1'34.979
15 Hector Barbera Ducati ESP 1'35.235
16 Mika Kalio Ducati FIN 1'35.810