Adapun Marc Marquez dari Repsol Honda masih belum mampu menunjukan performa terbaiknya.
Marc hanya berhasil bertengger di posisi ke-13 starting grid setelah sebelumnya sempat mengalami kecelakaan horor.
Berikut adalah daftar lengkap starting grid di MotoGP Spanyol 2021:
| POS | RIDER | NAT | TEAM | TIME/DIFF | LAP | MAX |
| 1 | Fabio Quartararo | FRA | Monster Yamaha (YZR-M1) | 1'36.755s | 7/7 | 288k |
| 2 | Franco Morbidelli | ITA | Petronas Yamaha (YZR-M1) | +0.057s | 3/8 | 287k |
| 3 | Jack Miller | AUS | Ducati Team (GP21) | +0.105s | 7/8 | 298k |
| 4 | Francesco Bagnaia | ITA | Ducati Team (GP21) | +0.205s | 8/8 | 296k |
| 5 | Takaaki Nakagami | JPN | LCR Honda (RC213V) | +0.253s | 3/8 | 287k |
| 6 | Johann Zarco | FRA | Pramac Ducati (GP21) | +0.299s | 7/7 | 294k |
| 7 | Maverick Viñales | SPA | Monster Yamaha (YZR-M1) | +0.315s | 3/8 | 288k |
| 8 | Aleix Espargaro | SPA | Aprilia Gresini (RS-GP) | +0.330s | 3/8 | 289k |
| 9 | Alex Rins | SPA | Suzuki Ecstar (GSX-RR) | +0.369s | 3/8 | 290k |
| 10 | Joan Mir | SPA | Suzuki Ecstar (GSX-RR) | +0.399s | 3/9 | 287k |
| 11 | Brad Binder | RSA | Red Bull KTM (RC16) | +0.712s | 4/4 | 288k |
| 12 | Stefan Bradl | GER | HRC (RC213V) | +0.747s | 8/8 | 292k |
| Qualifying 1: | ||||||
| 13 | Pol Espargaro | SPA | Repsol Honda (RC213V) | 1'37.407s | 6/8 | 292k |
| 14 | Marc Marquez | SPA | Repsol Honda (RC213V) | 1'37.489s | 2/7 | 291k |
| 15 | Enea Bastianini | ITA | Avintia Ducati (GP19)* | 1'37.675s | 8/8 | 293k |
| 16 | Miguel Oliveira | POR | Red Bull KTM (RC16) | 1'37.746s | 2/8 | 291k |
| 17 | Valentino Rossi | ITA | Petronas Yamaha (YZR-M1) | 1'37.915s | 6/8 | 284k |
| 18 | Luca Marini | ITA | Sky VR46 Avintia Ducati (GP19)* | 1'37.925s | 8/8 | 290k |
| 19 | Danilo Petrucci | ITA | KTM Tech3 (RC16) | 1'38.065s | 3/8 | 285k |
| 20 | Alex Marquez | SPA | LCR Honda (RC213V) | 1'38.069s | 6/8 | 290k |
| 21 | Iker Lecuona | SPA | KTM Tech3 (RC16) | 1'38.139s | 5/7 | 286k |
| 22 | Lorenzo Savadori | ITA | Aprilia Gresini (RS-GP)* | 1'38.325s | 2/7 | 286k |
| 23 | Tito Rabat | SPA | Pramac Ducati (GP21) | 1'38.641s | 3/8 | 287k |