Copa Libertadores 2017, Third qualifying stage |
 | 16.02.2017 | | Unión Española | – | The Strongest | | 1:1 (0:1) |
| Santiago |
Copa Libertadores 2014, Round of 16 |
| 24.04.2014 | | Arsenal | – | Unión Española | | 0:0 |
| Sarandí |
Copa Libertadores 2014, Group 2 |
| 12.03.2014 | | San Lorenzo de Almagro | – | Unión Española | | 1:1 (1:0) |
| Buenos Aires |
Copa Libertadores 2014, Group 2 |
| 26.02.2014 | | Unión Española | – | Botafogo | | 1:1 (0:0) |
| Santiago |
Copa Libertadores 2014, Group 2 |
| 18.02.2014 | | Independiente del Valle | – | Unión Española | | 2:2 (1:0) |
| Sangolquí |
Copa Libertadores 2012, Group 3 |
| 06.03.2012 | | Unión Española | – | Universidad Católica | | 1:1 (1:1) |
| Santiago |
Copa Libertadores 2012, Preliminary Round |
| 02.02.2012 | | Sinergia Deportiva | – | Unión Española | | 2:2 (2:1) |
| San Nicolás de los Garza |
Copa Libertadores 2011, Group 4 |
| 16.02.2011 | | Unión Española | – | Universidad Católica | | 2:2 (0:0) |
| Santiago |
Copa Libertadores 2011, Preliminary Round |
| 03.02.2011 | | Unión Española | – | Bolívar | | 0:0 |
| Santiago |
Copa Libertadores 2006, Group 3 |
| 19.04.2006 | | Goiás | – | Unión Española | | 0:0 |
| Goiânia |
Copa Libertadores 2006, Group 3 |
| 11.04.2006 | | Unión Española | – | Newell's Old Boys | | 1:1 (1:0) |
| Santiago |
Copa Libertadores 1994, Quarterfinal |
| 29.07.1994 | | Unión Española | – | São Paulo | | 1:1 (1:0) |
| Santiago |
Copa Libertadores 1994, 1/8 finals |
| 28.04.1994 | | Cruzeiro | – | Unión Española | | 0:0 |
| Belo Horizonte |
Copa Libertadores 1994, Group 4 |
| 12.04.1994 | | Defensor Sporting | – | Unión Española | | 1:1 (1:1) |
| Montevideo |
Copa Libertadores 1978, First Round, Group 3 |
| 19.04.1978 | | São Paulo | – | Unión Española | | 1:1 (0:0) |
| São Paulo |
Copa Libertadores 1978, First Round, Group 3 |
| 26.03.1978 | | Unión Española | – | São Paulo | | 1:1 (0:0) |
| Santiago |
Copa Libertadores 1978, First Round, Group 3 |
| 22.03.1978 | | Unión Española | – | Atlético-MG | | 1:1 (1:1) |
| Santiago |
Copa Libertadores 1978, First Round, Group 3 |
| 14.03.1978 | | Unión Española | – | Palestino | | 0:0 |
| Santiago |
Copa Libertadores 1976, First Round, Group 5 |
| 31.03.1976 | | Nacional Montevideo | – | Unión Española | | 1:1 (1:0) |
| Montevideo |
Copa Libertadores 1976, First Round, Group 5 |
| 13.03.1976 | | Unión Española | – | Peñarol | | 0:0 |
| Santiago |
Copa Libertadores 1975, Semifinal group 1 |
| 03.06.1975 | | Universitario de Deportes | – | Unión Española | | 1:1 (1:0) |
| Lima |
Copa Libertadores 1975, First Round, Group 2 |
| 16.03.1975 | | The Strongest | – | Unión Española | | 1:1 (0:1) |
| La Paz |
Copa Libertadores 1975, First Round, Group 2 |
| 12.03.1975 | | Jorge Wilstermann | – | Unión Española | | 1:1 (1:0) |
| Cochabamba |
Copa Libertadores 1975, First Round, Group 2 |
| 26.02.1975 | | Huachipato | – | Unión Española | | 0:0 |
| Concepción |
Copa Libertadores 1973, First Round, Group 3 |
| 24.03.1973 | | Unión Española | – | Emelec | | 1:1 (1:0) |
| Santiago |
Copa Libertadores 1973, First Round, Group 3 |
| 18.03.1973 | | Unión Española | – | Colo-Colo | | 0:0 |
| Santiago |
Copa Libertadores 1971, First Round, Group 4 |
| 31.03.1971 | | Unión Española | – | Colo-Colo | | 1:1 (0:0) |
| Santiago |
Copa Libertadores 1971, First Round, Group 4 |
| 20.03.1971 | | Unión Española | – | Cerro Porteño | | 0:0 |
| Santiago |
Copa Libertadores 1971, First Round, Group 4 |
| 18.02.1971 | | Guaraní Asunción | – | Unión Española | | 1:1 (0:0) |
| Asunción |
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