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Technically, I think the answer is 'neither'. Though in certain circumstances, either could get the benefit. Let me explain better...
There could be as many as 4 characters involved in this, or as few as 2. You couldn't have 1 because you are not your own ally.
The first thing to note about the wording is that this is the activated ability of an item. So when it refers to 'you' it is meaning the character that is wielding the item.
So when it says 'you or an adjacent willing creature' that means the character wielding the item or a character adjacent to that character with the item.
The other thing to note is that the reaction does not require that you are the one doing the healing. Though it is possible to trigger the reaction if you are the one doing the healing.
So this is the proper answer to the question: If an adjacent creature is the one benefitting from the reaction (instead of 'you'), then it must be one that is adjacent to the character wielding the item. Not necessarily the creature being healed or the one doing the healing.
Specific examples. Tim is the target being healed. You and Harry can both cast targeted healing spells such as Heal or Soothe. You are the one wielding the item with Vitality Siphon. Bob is a bystander/ally standing adjacent to you. You are not adjacent to Tim or Harry. Everyone is down a few HP.
2-person scenario: You heal Tim for more HP than he is down. You trigger the Vitality Siphon reaction and give yourself the excess.
3-person scenario 1: You heal Tim. You trigger the Vitality Siphon reaction and give Bob the excess. You can't give Harry the excess because he is not adjacent to you, and you wouldn't want to target Tim because he is now full on HP.
3-person scenario 2: Harry heals Tim. You trigger the Vitality Siphon reaction and give yourself the excess.
4-person scenario: Harry heals Tim. You trigger the Vitality Siphon reaction and give Bob the excess.