PokéBase - Pokémon Q&A
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Btw your question is a little vague and invalid but I'll try to answer it and plus this includes things which happen after you catch all the Pokemon even the ones in the National Dex.
According to Bulbapedia:
In GEN 1 games:
- You got a Diploma.
In Gen 2 games (Gold, Silver and Crystal):
- You got a Diploma:
In Gen 3 games:
- You could choose Johto starters (Emerald only)
- You got a Diploma

In Gen 4:
- Diploma!
- You could unlock the national Dex by seeing all the Pokemon.
In Gen 5:
- Oval Charm by catching all the Pokemon in Unova
- Shiny Charm for completing the National Dex (if that counts)
- You can go to Nature Reserve once you have seen all the Unova Pokemon
to catch a shiny Haxorus (BW2 only)
- and A Diploma

Gen 6 (XY,ORAS):
- Oval charm for seeing all the Pokemon in Kalos/Hoenn depending on which game you're playing.
- Shiny Charm for completing the National Pokedex (Both games)
- And of course! A game isn't complete without a Diploma!

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I may be mistaken, but I believe all core games from Gen 4 forward has post game content based on completing the national dex (though there are exclusions of mythical Pokemon). Emerald allows Chikorita, Cyndaquil or Totodile.

Diamond, Pearl, Platinum
Black, White, Heart Gold, Soul Silver, Black 2, White 2,
X, Y, Omega Ruby, Alpha Sapphire

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Other games have an upgrade, but not necessarily upon completion