Few things kill a peach pie faster than flabby, long-cooked skin. Luckily, peeling peaches is far less daunting than it may appear on the outset. A few quick steps are all that separate an exceptional peach pie  from a total flop.
Score the Skin
Use a sharp paring knife to score the skin, by making a very shallow cut (avoid marring the flesh as much as possible) into the pointed end of each peach, in an x-shape. This will aid the peeling process later on.
Simmer the Peaches
Dunk the peaches into a bath of simmering water that is deep enough to submerge them completely. If the peaches do not stay submerged, turn them occasionally, so that they are heated evenly. After about 40 seconds (a minute if they're slightly underripe), or when the skin begins to slightly pull away on the scored ends, remove the peaches with a slotted spoon or skimmer.
Cool the Peaches Down
Submerge the peaches in a bowl of ice water, and allow them to cool completely. Don't skip this step, as it's important to cool the peaches down quickly, in order to stop the cooking process, so that they don't become mushy.
Peel the Peaches
Gently peel the peaches by pulling at the skin or rubbing it off gently with the side or pad of your thumb. The skin should come off easily; if it does not, simmer the peaches slightly longer, chill them down, and try again.