Corrected entry: When Nathan and Rick throw the knife and stab Leo after Leo pulls the knife out he heals himself, However throughout the whole series Leo makes it clear that Whitelighters can't heal themselves.
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Correction: It's been noted throughout the series that the only way to kill a whitelighter is with the poison from a darklighter's arrow. Leo can't heal himself when injured from a darklighter, but can heal himself from other wounds.
Wait that still doesn't make sense. In the episode where Piper and Phoebe find out about Paige's existence, Leo gets injured and Phoebe asks him why he cannot heal himself and he responds "3 years together and you are just now asking these questions?" Piper is icing his neck for him. That was another wound (not from a darklighter) and he was not able to heal himself then. I think the writers just needed an easy way to show the ghost brothers that Leo was still alive and that he is a whitelighter that cannot die.