Note that the gains of EV's are applied when leveling so a level 100 pokemon won't gain anythig from EV's anymore. Finish up collecting all EV's by level 99.
Well technically you can...but it's a very erritating process so...yeah, I'm gonna just go with this...besides, I don't see someone actually needing to EV train at any level that's above 90 but that's me...&...good Joeyboy, just be sure not to trust those results too much til it hits lv. 50 as most pokemon at that level & higher tend to give you exact results most of the time...
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"The Nine Tails of Subconscious - Lawence Codye"