| 2021-07-26 | Kitzbuhel | Clay | R16 | 14 | Casper Ruud (1) | 167 | Mario Vilella Martinez (LL) | 7-5 5-7 6-4 | H2H | 3 | 139 | 4 | 7 | 55.6% | 76.0% | 65.0% | 0/2 |
| 2021-07-26 | Kitzbuhel | Clay | R32 | 167 | Mario Vilella Martinez (LL) | 980 | Lukas Neumayer (Q) | 6-7(4) 7-5 6-4 | H2H | 3 | 167 | 7 | 10 | 51.3% | 78.3% | 45.6% | 7/10 |
| 2021-05-31 | Roland Garros | Clay | R128 | 11 | Roberto Bautista Agut (11) | 183 | Mario Vilella Martinez (Q) | 6-4 6-4 6-2 | H2H | 5 | 118 | 2 | 2 | 63.2% | 81.4% | 76.0% | 3/4 |
| 2021-04-05 | Marbella | Clay | R16 | 15 | Pablo Carreno Busta (1) | 188 | Mario Vilella Martinez (Q) | 7-6(2) 6-3 | H2H | 3 | 97 | 3 | 0 | 70.8% | 72.5% | 61.9% | 2/2 |
| 2021-04-05 | Marbella | Clay | R32 | 188 | Mario Vilella Martinez (Q) | 146 | Bernabe Zapata Miralles (Q) | 6-2 6-3 | H2H | 3 | 80 | 4 | 3 | 66.0% | 72.7% | 52.9% | 3/4 |
| 2021-02-08 | Australian Open | Hard | R128 | 199 | Tomas Machac (Q) | 181 | Mario Vilella Martinez (Q) | 6-7(5) 7-5 6-0 3-0 RET | H2H | 5 | 152 | 11 | 1 | 65.3% | 79.7% | 55.9% | 5/6 |
| 2021-02-01 | Great Ocean Road Open | Hard | R16 | 52 | Jordan Thompson (11) | 188 | Mario Vilella Martinez | 6-4 6-4 | H2H | 3 | 84 | 2 | 2 | 67.2% | 76.7% | 61.9% | 8/8 |
| 2021-02-01 | Great Ocean Road Open | Hard | R32 | 188 | Mario Vilella Martinez | 39 | Nikoloz Basilashvili (5) | 7-5 6-3 | H2H | 3 | 94 | 13 | 5 | 55.0% | 75.0% | 55.6% | 8/9 |
| 2021-02-01 | Great Ocean Road Open | Hard | R64 | 188 | Mario Vilella Martinez | 101 | Yannick Hanfmann | 7-6(2) 6-4 | H2H | 3 | 98 | 8 | 8 | 46.3% | 76.3% | 56.8% | 4/5 |
| 2020-01-20 | Australian Open | Hard | R128 | 17 | Karen Khachanov (16) | 195 | Mario Vilella Martinez (Q) | 4-6 6-4 7-6(4) 6-3 | H2H | 5 | 170 | 10 | 1 | 63.5% | 80.8% | 71.4% | 1/2 |