No, the pokemon holding exp share only gets the normal EVs. PKRS can let you get double the EVs if it is holding experience share though.
Also, if you lead with the pokemon you want to ev train (with PKRS and the proper Power Item) you can switch out to a high level pokemon and KO the specific ev pokemon you want and your pokemon will get all the evs it needs.
For example, if you want to EV your Chansey/Happiny in Special Defense. Infect it with PKRS and give it a Power Band and place it at the front of your team. You surf around in the southern most sea until you find a tentacool. Chansey is tossed out. Switch to a level 100 or whatever and KO the jellyfish. Chansey will get 10 EVs in Special Defense without doing anything.