The Pescarolo number 16, driven by Erik Comas, Jean-Christophe Boullion and Emmanuel Collard, has snatched pole position for the Le Mans 24-hour race.
Ayari is joined by Eric Helary and Sebastien Loeb in his Pescarolo car
The all-French team clocked three minutes 34.715 seconds in final qualifying on Thursday.
The Pescarolo number 17 driven by Sebastien Loeb, Eric Helary and Soheil Ayari was 0.84 seconds behind.
Italian Emanuele Pirro, German Frank Biela and Briton Alan McNish were three seconds off the pace in their Audi.
Dane Tom Kristensen, gunning for a record seventh victory in the world's most famous endurance race, struggled to eighth in another Audi with Finn JJ Lehto and German Marco Werner.
The Dome Mugen, driven by Japanese Ryo Michigami, Seiji Ara and Katsutomo Kaneishi, surprisingly came home fourth.
Another Audi, with Renault Formula One test driver Franck Montagny, Jean-Marc Gounon and Stephane Ortelli, finished fifth.
Aston Martin took first blood in the battle with Corvette for honours in the GT1 category for modified road cars.
The DB9 of Czech Tomas Enge, Dutchman Peter Cox and Portugal's Pedro Lamy was fastest in a time of three minutes 48.576 seconds, beating its sister car by just over a second.
The fastest Corvette - that of Briton Oliver Gavin, Monegasque Olivier Beretta and Dane Jan Magnussen - was nearly four seconds adrift.
Le Mans qualifying times:
1.Emmanuel Collard, Jean-Christophe Boullion, Erik Comas - Pescarolo 3 minutes 34.715 seconds
2. Sebastien Loeb, Eric Helary, Soheil Ayari - Pescarolo 3:35.555
3. Emanuele Pirro, Frank Biela, Alan McNish - Audi 3:37.795
4. Ryo Michigami, Seiji Ara, Katsutomo Kaneishi - Dome Mugen 3:38.095
5. Franck Montagny, Jean-Marc Gounon, Stephane Ortelli - Audi 3:38.281
6. Jonathan Cochet, Shinji Nakano, Bruce Jouanny / Courage 3:38.735
7. Nicolas Minassian, Jamie Campbell-Water, Andy Wallace - DBA 3:38.929
8. Tom Kristensen, JJ Lehto, Marco Werner - Audi 3:38.998
9. Martin Short, Joao Barbosa, Vanina Ickx - Dallara 3:39.643
10. Sam Hignett, John Robert Stack, Haruki Kurosawa - Zytek 3:41.177
13. D Schwager, A Frei, C Vann - Courage Judd 3:42.589
14. RG Verdoen Roe, M Krumm, H Primat - Dallara 3:43.377
15. G Fisken, E Halliday, S Hancock - Lola AER 3:44.752
16. T Erdos, M Newton, W Hughes - Lola MG 3:46.205
19. P Bennett, I Mitchell, T Mullen - Courage Judd 3:49.267
20. D Brabham, S Sarrazin, D Turner - Aston Martin D 3:49.739
21. S Zlobin, B Briere, J Barazi - Courage AER 3:51.844
22. O Gavin, O Beretta, J Magnussen - Corvette C6-R 3:52.426
24. CY Gosselin, K Ojjeh, A Sharpe - Courage C65 Fo 3:35.376
26. R Evans, R Berridge, P Owen - Lola AER 3:55.531
27. R Fellows, J O'Connell, M Papis - COrvette C6-R 3:55.914
31. Y Terada, P Roussel, W Binnie - WR Peugeot 3:59.103
36. B Auberlen, R Liddell, SC Maxwell - Panoz Elan 4:07.027
43. N Kinch, A Kirkaldy, A Reid - Ferrari 360 Mo 4:13.237
45. J Macari, S Ericsson, R Wilson - Ferrari 360 Mo 4:20.873
46. J Hartshorne, R Stanton, P Johnson - TVR Tuscan T40 4:22.310
48. V Hillebrand, F Hahn, G Pickering - Courage C65 Ju 4:31.453
There will be regular updates from Le Mans on the BBC Sport website. The race starts at 1500 BST on Saturday 18 June.