If both go into battle, yes. I know from experience... the first Pokemon I tried to train EVs was a Pichu. I intended to raise his level to 20 and then starting to train his EVs. I put the EXP. Share on him and started to level up his level. When I went to train his EV, I realized that he had already received EVs even without battling. Searching, I found that the EXP. Share also shared the base EV. That was sad, but at least it was a lesson... X'D