1968 Summer Olympics |
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| Bantamweight, Men | Alex Martínez | 13 | |
| Lightweight, Men | Valerio Fontanals | AC | |
1996 Summer Olympics |
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| Featherweight, Men | Francisco Cáceres | 31 | |
2000 Summer Olympics |
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| Light-Heavyweight, Women | Eva Dimas | 12 | |
2004 Summer Olympics |
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| Heavyweight, Women | Eva Dimas | 11 | |
2008 Summer Olympics |
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| Super-Heavyweight, Women | Eva Dimas | DNF | |
2012 Summer Olympics |
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| Featherweight, Men | Julio César Salamanca | 10 | |
2016 Summer Olympics |
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| Featherweight, Men | Julio César Salamanca | 10 |