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In Pokemon Diamond and Pearl you can catch an Eevee by going to Mr.Backlot's mansion on route 212 between Hearthome City and Pastoria's Great Marsh. You can talk to him in his office and he will talk about his trophy garden, just say you're envious and he will mention a Pokemon that will then appear in his garden for a day. Sometimes he will mention Eevee. I suggest you save before talking to him and keep reloading the game until he mentions Eevee is in the garden, when he does you can catch Eevee there for a while, but it's quite rare so you have to be patient. I have Eevee and all of it's evolved forms. :-) Komanoto998 - There is an easier way. Complete the game, then go to Hearthome City. Talk to Bebe (she's in charge of the PkMn SYSTEM), and she'll give you a Eevee (Lv. 5). I did, breeded it with Ditto, evolved them into different forms, laughed(haha!) and now i have all of its Evo.s.
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