4th Gen best EV spots

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Taken directly from the stickied FAQ:

Shiny Umbreon said:
Wild Pokémon

HP
Route 212 (Pastoria Side). While surfing, you can find many Wooper (1 HP) and some Quagsire (2 HP).
In the ground, Wooper (1 HP) and Bibarel (2 Attack) are very common there. Although there are Kricketune (2 Attack) and Roselia (2 Sp. Atk) too.
Fuego Ironworks. Gastrodon (2 HP) and Shellos (1HP) can be found here while Wingull (1 Speed), Shinx (1 Attack), Luxio (2 Attack) and Pachirisu (1 Speed) should be ignored.
Route 221. In Pearl, Gastrodon (2 HP) will be pretty common and there will be Sudowoodo (2 Defense). In Diamond, some Gastrodon (2 HP) are replaced by Stunky (1 Speed) and Skuntank (2 HP) The rest are Roselia (2 Sp. Attack), Shellos (1 HP), Floatzel (2 Speed) and Wingull (1 Speed).

Attack
Route 229. Gyarados (2 Attack) are the only Pokémon to be found while fishing.
Twinleaf Town. While fishing with super rod, Gyarados (2 Attack) and Seaking (2 Attack) are the only Pokémon to be found.
Route 210 (Celestic Side). You will find Bibarel (2 Attack), Machop (1 Attack) and Machoke (2 Attack) at the same rate as Psyduck (1 Sp. Attack), Meditite (Speed), Hoothoot (1 HP) and Noctowl (2 HP). Note that during the morning and day, Hoothoot and Noctowl will be replaced by Meditite, making it the most common.

Defense
Ruin Maniac Cave. Geodude (1 Defense) are the most common, and the only other Pokémon here is Hippopotas (1 Defense).
Iron Island B2F (Riley's Room)/B3F. The common Pokémon here are Graveler (2 Defense) and Onix (1 Defense), with the other being Golbat (2 Speed), Steelix (2 Defense) and Geodude (1 Defense), who almost never appears.
Oreburgh Mine. Geodude (1 Defense) are common here. You can also find Onix (1 Defense) and Zubat (1 Speed) a bit less often.

Sp. Attack
Old Chateau. Gastly (1 Sp. Attack) are the only Pokémon found here while any GBA game in Slot 2 allows you to rarely find Haunter (2 Sp. Attack) and Gengar (3 Sp. Attack). The latter is only at the room with the eyes on the wall.
Resort Area. When surfing, Golduck (2 Sp. Attack) can be found.
Route 204. When surfing, Psyduck (1 Sp. Attack) appears often with Golduck (2 Sp. Attack) ocassionally.

Sp. Defense
Route 223. Tentacruel (2 Sp. Defense) and Pelipper (2 Defense) are common, while there are few Mantyke (1 Sp. Defense). Tentacruel seem to be more common, though.
Any other surfing area. The most common Pokémon is Tentacool (1 Sp. Defense).

Speed
Route 226. There's plenty of Fearow and Raticate (2 points each) and sometimes Spearow and Rattata (1 point each). You may rarely find Machoke (2 Attack) or Golduck (2 Attack). It's better at day, because Banette (2 Attack) appear frequently at night.
Victory Road B1F. When surfing, Golbat (2 Speed) are the only Pokémon to be found.
Trophy Garden. Though Roselia (2 Sp. Attack) are more common that others, there are Pichu (1 Speed), Pikachu (2 Speed), Staravia (2 Speed) and Kricketune (2 Attack). Note that, during the morning, Pichu are more common; in the day, Staravia; and during the night, Kricketune; though neither of these affect the number of Roselia.
Route 221. In Pearl, Gastrodon (2 HP) will be pretty common and there will be Sudowoodo (2 Defense). In Diamond, some Gastrodon (2 HP) are replaced by Stunky (1 Speed) and Skuntank (2 HP) The rest are Roselia (2 Sp. Attack), Shellos (1 HP), Floatzel (2 Speed) and Wingull (1 Speed).
 
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