Yes, catching a Pokémon will give out EVs as long as EXP is earned as well.
Since any Pokémon gaining experience points gains EVs, the Exp. Share item allows Pokémon to gain EVs without battling. It will gain the same base EVs that the Pokémon in battle gains. The Pokémon holding Exp. Share will benefit from its own Pokérus (see below), but not from the item or condition of the Pokémon in battle.
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