13:00 – lørdag 21 september, 2019
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| Villarreal | 2-0 | Real Valladolid |
Fuldtid
 | ||
| 2-0 Javi Ontiveros |  | 89' |
| 80' |  | Pablo Hervías Míchel |
1-0 Santi Cazorla Straffespark |  | 77' |
| 74' | | Anuar Tuhami Óscar Plano |
Javi Ontiveros Vicente Iborra | | 74' |
| 66' | | Waldo Rubio Sandro Ramírez |
Samuel Chukwueze Moi Gómez | | 66' |
| 60' |  | Federico Barba |
Karl Toko Ekambi Carlos Bacca | | 58' |
| Vicente Iborra | | 45' |
| Pause 0-0 | ||
| Xavi Quintillà | | 40' |
| ||