Yes, the skins will peel off quite easily after canning, much like peach or tomato skins peel off after blanching.
And yes, it is safe to can them with the skins on. Peeling peaches, pears, and the rest is a cosmetic choice. The acidity of the fruit is sufficient for it to be safe. If you were worried about it, though, you could add a teaspoon of lemon juice to each jar, to be sure.
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