Sedangkan Valentino Rossi, sejak awal sudah otomatis lolos Q2.
Tetapi sayangnya The Doctor tidak bisa memanfaatkan kesempatan emas itu.
Ia justru mengalami crash di tikungan 4 sirkuit Barcelona setelah percobaan pertamanya di kualifikasi.
Mixed fortunes for @sepangracing! ????@FrankyMorbido12 is up in P2 but @ValeYellow46 has tumbled at Turn 4! ????#CatalanGP ???? pic.twitter.com/VKRnySZU22
— MotoGP™???? (@MotoGP) June 5, 2021
Pada percobaan kedua, catatan waktu Rossi masih belum bisa mengejar para pembalap lain.
Rossi menempati posisi ke-11.
Berikut hasil akhir kualifikasi MotoGP Catalunya 2021.
| POS. | PEMBALAP | TIM | WAKTU/GAP | LAP. |
| 1 | Fabio Quartararo | Monster Yamaha (YZR-M1) | 1'38.853s | 3/7 |
| 2 | Jack Miller | Ducati Team (GP21) | +0.037s | 5/5 |
| 3 | Johann Zarco | Pramac Ducati (GP21) | +0.196s | 8/8 |
| 4 | Miguel Oliveira | Red Bull KTM (RC16) | +0.246s | 8/8 |
| 5 | Franco Morbidelli | Petronas Yamaha (YZR-M1) | +0.256s | 8/8 |
| 6 | Maverick Viñales | Monster Yamaha (YZR-M1) | +0.304s | 8/8 |
| 7 | Aleix Espargaro | Aprilia Gresini (RS-GP) | +0.365s | 7/8 |
| 8 | Brad Binder | Red Bull KTM (RC16) | +0.490s | 6/8 |
| 9 | Francesco Bagnaia | Ducati Team (GP21) | +0.506s | 8/8 |
| 10 | Joan Mir | Suzuki Ecstar (GSX-RR) | +0.578s | 6/8 |
| 11 | Valentino Rossi | Petronas Yamaha (YZR-M1) | +0.752s | 6/6 |
| 12 | Pol Espargaro | Repsol Honda (RC213V) | +2.938s | 2/2 |
| Kualifikasi 1 (Q1) | ||||
| 13 | Marc Marquez | Repsol Honda (RC213V) | 1'39.181s | 7/7 |
| 14 | Takaaki Nakagami | LCR Honda (RC213V) | 1'39.347s | 7/8 |
| 15 | Jorge Martin | Pramac Ducati (GP21) | 1'39.532s | 7/7 |
| 16 | Iker Lecuona | KTM Tech3 (RC16) | 1'39.567s | 2/5 |
| 17 | Enea Bastianini | Avintia Ducati (GP19) | 1'39.59s | 7/7 |
| 18 | Danilo Petrucci | KTM Tech3 (RC16) | 1'39.744s | 7/7 |
| 19 | Luca Marini | Sky VR46 Avintia Ducati (GP19) | 1'39.942s | 7/8 |
| 20 | Alex Marquez | LCR Honda (RC213V) | 1'40.009s | 8/8 |
| 21 | Lorenzo Savadori | Aprilia Gresini (RS-GP) | 1'40.158s | 6/6 |