To smite (kill) another player, you first have to be in melee range of them. Then simply attack them by left clicking until they die.
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the smite enchantment in minecraft makes it so your sword does extra damage do zombies, skeletons and pigmen.
If you're talking about the smite enchantment, then no. Smite affects Zombies and Skeletons.
It makes lighting hit the player that you entered into the /smite command
Smite increases damage against zombies, skeletons and zombie pigmen.
Smite is an enchantment you can put on swords. With it, you can do extra damage to zombies, zombie pigmen, and skeletons.