Qualified Teams
| Country | Team | Qualification method |
|---|---|---|
| CONMEBOL |
Independiente | 1965 Copa de Campeones winners |
| Argentina |
Boca Juniors | 1965 Primera División champion |
| River Plate | 1965 Primera División runner-up | |
| Bolivia |
Deportivo Municipal | 1965 Copa Simón Bolívar champion |
| Jorge Wilstermann | 1965 Copa Simón Bolívar runner-up | |
| Chile |
Universidad de Chile | 1965 Primera División champion |
| Universidad Católica | 1965 Primera División runner-up | |
| Ecuador |
Emelec | 1965 Campeonato Ecuatoriano de Fútbol champion |
| 9 de Octubre | 1965 Campeonato Ecuatoriano de Fútbol runner-up | |
| Paraguay |
Olimpia | 1965 Primera División champion |
| Guaraní | 1965 Primera División runner-up | |
| Peru |
Alianza Lima | 1964 Primera División champion |
| Universitario | 1964 Primera División runner-up | |
| Uruguay |
Peñarol | 1964 Primera División champion |
| Nacional | 1964 Primera División runner-up | |
| Venezuela |
Lara FC | 1965 Venezuelan Primera División champion |
| Deportivo Italia | 1965 Venezuelan Primera División runner-up |
Read more about this topic: 1966 Copa Libertadores
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