| Jornada 1 | 18/08/2013 | RAYO VALLEC. | 3 | ELCHE | 0 |
| Jornada 2 | 25/08/2013 | ATLETICO MADRID | 5 | RAYO VALLEC. | 0 |
| Jornada 3 | 01/09/2013 | RAYO VALLEC. | 1 | LEVANTE | 2 |
| Jornada 4 | 15/09/2013 | MALAGA | 5 | RAYO VALLEC. | 0 |
| Jornada 5 | 22/09/2013 | RAYO VALLEC. | 0 | FC BARCELONA | 4 |
| Jornada 6 | 25/09/2013 | SEVILLA | 4 | RAYO VALLEC. | 1 |
| Jornada 7 | 29/09/2013 | VALENCIA | 1 | RAYO VALLEC. | 0 |
| Jornada 8 | 06/10/2013 | RAYO VALLEC. | 1 | REAL SOCIEDAD | 0 |
| Jornada 9 | 20/10/2013 | ALMERIA | 0 | RAYO VALLEC. | 1 |
| Jornada 10 | 27/10/2013 | RAYO VALLEC. | 0 | VALLADOLID | 3 |
| Jornada 11 | 30/10/2013 | OSASUNA | 3 | RAYO VALLEC. | 1 |
| Jornada 12 | 03/11/2013 | RAYO VALLEC. | 2 | REAL MADRID | 3 |
| Jornada 13 | 10/11/2013 | CELTA | 0 | RAYO VALLEC. | 2 |
| Jornada 14 | 24/11/2013 | RAYO VALLEC. | 1 | ESPANYOL | 4 |
| Jornada 15 | 01/12/2013 | BETIS | 2 | RAYO VALLEC. | 2 |
| Jornada 16 | 15/12/2013 | RAYO VALLEC. | 0 | GRANADA | 2 |
| Jornada 17 | 22/12/2013 | ATHLETIC BILBAO | 2 | RAYO VALLEC. | 1 |
| Jornada 18 | 05/01/2014 | RAYO VALLEC. | 2 | VILLARREAL | 5 |
| Jornada 19 | 12/01/2014 | GETAFE | 0 | RAYO VALLEC. | 1 |
| Jornada 20 | 19/01/2014 | ELCHE | 2 | RAYO VALLEC. | 0 |
| Jornada 21 | 26/01/2014 | RAYO VALLEC. | 2 | ATLETICO MADRID | 4 |
| Jornada 22 | 02/02/2014 | LEVANTE | 0 | RAYO VALLEC. | 0 |
| Jornada 23 | 09/02/2014 | RAYO VALLEC. | 4 | MALAGA | 1 |
| Jornada 24 | 16/02/2014 | FC BARCELONA | 6 | RAYO VALLEC. | 0 |
| Jornada 25 | 23/02/2014 | RAYO VALLEC. | 0 | SEVILLA | 1 |
| Jornada 26 | 02/03/2014 | RAYO VALLEC. | 1 | VALENCIA | 0 |
| Jornada 27 | 09/03/2014 | REAL SOCIEDAD | 2 | RAYO VALLEC. | 3 |
| Jornada 28 | 16/03/2014 | RAYO VALLEC. | 3 | ALMERIA | 1 |
| Jornada 29 | 23/03/2014 | VALLADOLID | 1 | RAYO VALLEC. | 1 |
| Jornada 30 | 26/03/2014 | RAYO VALLEC. | 1 | OSASUNA | 0 |
| Jornada 31 | 30/03/2014 | REAL MADRID | 5 | RAYO VALLEC. | 0 |
| Jornada 32 | 06/04/2014 | RAYO VALLEC. | 3 | CELTA | 0 |
| Jornada 33 | 13/04/2014 | ESPANYOL | 2 | RAYO VALLEC. | 2 |
| Jornada 34 | 20/04/2014 | RAYO VALLEC. | 3 | BETIS | 1 |
| Jornada 35 | 27/04/2014 | GRANADA | 0 | RAYO VALLEC. | 3 |
| Jornada 36 | 04/05/2014 | RAYO VALLEC. | 0 | ATHLETIC BILBAO | 3 |
| Jornada 37 | 11/05/2014 | VILLARREAL | 4 | RAYO VALLEC. | 0 |
| Jornada 38 | 18/05/2014 | RAYO VALLEC. | 1 | GETAFE | 2 |