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Vítězem kvalifikace na Velkou cenu Španělska se stal Nico Rosberg s vozem Mercedes, druhé místo obsadil jeho stájový kolega Nico Rosberg a třetí skončil Sebastian Vettel.
| P | # | Jezdec | Konstruktér | Q1 | Q2 | Q3 | K | |
|---|---|---|---|---|---|---|---|---|
| 1 | 9 | Nico Rosberg | Mercedes | 1:21.913 | 1:21.776 | 1:20.718 | 12 | |
| 2 | 10 | Lewis Hamilton | Mercedes | 1:21.728 | 1:21.001 | 1:20.972 | 12 | |
| 3 | 1 | Sebastian Vettel | Red Bull | 1:22.158 | 1:21.602 | 1:21.054 | 12 | |
| 4 | 7 | Kimi Räikkönen | Lotus | 1:22.210 | 1:21.676 | 1:21.177 | 17 | |
| 5 | 3 | Fernando Alonso | Ferrari | 1:22.264 | 1:21.646 | 1:21.218 | 12 | |
| 6 | 4 | Felipe Massa | Ferrari | 1:22.492 | 1:21.978 | 1:21.219 | 12 | |
| 7 | 8 | Romain Grosjean | Lotus | 1:22.613 | 1:21.998 | 1:21.308 | 16 | |
| 8 | 2 | Mark Webber | Red Bull | 1:22.342 | 1:21.718 | 1:21.570 | 12 | |
| 9 | 6 | Sergio Pérez | McLaren | 1:23.116 | 1:21.790 | 1:22.069 | 13 | |
| 10 | 14 | Paul di Resta | Force India | 1:22.663 | 1:22.019 | 1:22.233 | 17 | |
| 11 | 19 | Daniel Ricciardo | Toro Rosso | 1:22.905 | 1:22.127 | 14 | ||
| 12 | 18 | Jean–Éric Vergne | Toro Rosso | 1:22.775 | 1:22.166 | 12 | ||
| 13 | 15 | Adrian Sutil | Force India | 1:22.952 | 1:22.346 | 12 | ||
| 14 | 5 | Jenson Button | McLaren | 1:23.166 | 1:22.355 | 9 | ||
| 15 | 11 | Nico Hülkenberg | Sauber | 1:23.058 | 1:22.389 | 13 | ||
| 16 | 12 | Esteban Gutiérrez | Sauber | 1:23.218 | 1:22.793 | 15 | ||
| 17 | 17 | Valtteri Bottas | Williams | 1:23.260 | 9 | |||
| 18 | 16 | Pastor Maldonado | Williams | 1:23.318 | 9 | |||
| 19 | 21 | Giedo van der Garde | Team Caterham | 1:24.661 | 6 | |||
| 20 | 22 | Jules Bianchi | Marussia | 1:24.713 | 6 | |||
| 21 | 23 | Max Chilton | Marussia | 1:24.996 | 6 | |||
| 22 | 20 | Charles Pic | Team Caterham | 1:25.070 | 6 |
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