I use this method of peeling peaches when I'm making something that requires lots of skinless peach sections. Boil a large pot of water. Carefully drop the peaches into the boiling water and allow to sit in there for 20 seconds or so. The skin will begin to split. Remove peaches with slotted spoon and drop into an ice bath. After 10 seconds, grab the peach and pinch the skin with your fingers. The skin will slip off easily. I also use this method for peeling tomatoes.
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The easiest way to peel a lot of peaches for canning or freezing is to bring a large pot of water to a boil and fill the kitchen sink with cold water.
The best way to peel peaches, especially if you have a lot of them, is to boil some water and drop them gently into the hot water with a slotted spoon. Let them stay in the hot water for about 1 minute, pull them out, and cool them under cold running water.
