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Sorry for the confusing title. It's a long question with weird words, and I'm just trying EV training for the first time. I think I get the basics, but I'm stumped by this question.

I have an Azelf in a playthrough, and I want to EV train it for Attack and Special Attack. The only thing is, I've already used it in a couple battles and wasn't keeping track of the EV's gained yet. I caught it at Lv. 50 and it's at Lv. 53. So whatever's left, I want to go to Attack and Special Attack. I'm training in Attack first by repeatedly battling a dude with 3 Machop on Route 215 for 6 Attack EV's a pop, but what I want to know is...

If Azelf's Attack EV's are eventually maxed out at 255, and Azelf obviously hasn't cashed out all 510 of it's EV's, and I keep fighting Machop that only give Attack EV's, am I at a point where Azelf gets Exp. but not EV's? Or is Azelf still collecting EV's that it can't use? Or is something else happening all together? I thought these games were meant for kids.

I'm trying to do a lot of things right now, and one of those things is not taking this super seriously, so I'm not keeping a spreadsheet on Azelf's battles or anything like that, but I can't stop thinking about this question, and I'm having trouble finding information about it. Thank you if you take time to skim this and leave any answer, and have a wonderful day.

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If Azelf's Attack EV's are eventually maxed out at 255, and Azelf obviously hasn't cashed out all 510 of it's EV's, and I keep fighting Machop that only give Attack EV's, am I at a point where Azelf gets Exp. but not EV's?

Yes, once a Pokemon reaches max EV's in a stat they cannot increase any further. So if you have 255 attack EVs, fighting Machop will only give you experience.

Or is Azelf still collecting EV's that it can't use?

It isn't, but if you're fighting a Pokemon that gives you EVs in multiple stats (say attack and speed), then you'll gain EVs in Speed but not Attack.

To get rid of EVs in stats you don't want, use the respective Berries. They increase friendship but lower EVs in a specific stat. Since they reduce to 100 with the first use (if you are above 100) then 10 from there, you only ever need to use 11 of the berries to completely reduce EVs in a stat to zero.

The berries for each stat are:

  • Pomeg Berry (HP)

  • Kelpsy Berry (Attack)

  • Qualot Berry (Defense)

  • Hondew Berry (Sp. Attack)

  • Grepa Berry (Sp. Defense)

  • Tamato Berry (Speed)

Source: Experience and this.

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You can have 252 as a max ev in one stat, not 255
252 is the max that has any effect, but 255 is the true maximum.
Interesting