I prefer to poach, then peel. Firstly, once poached, the peels slip off and leave a pristine peach behind. If you blanch and peel, you're bound to blemish and bruise and just wind up handling it a bit rougher than if its poached, cooled and rested. Secondly the color is key. Your poaching liquid will elicit the kind of oohs and ahhs you deserve for serving such a classy end to a meal.
Please do peel them before poaching. I would blanch them first in a big pot of boiling water for no more than a minute or two. If you make a little cross in the bottom end of the peeling, the skin should slip off then.
I've seen peaches poaches with their skin in. Once you are done poaching, removed the peaches for the liquid and the skin should slip right off. You can then leave the skin in the liquid until the liquid has come to room temperature (the skin helps to color the liquid). Remove all the solids from the liquid and make a granita with it!
Typically, you would make a small "x" in the bottom of peach and then blanche for about a minute in boiling water, then remove and slip the skins off, then halve and remove pits if the instructions say to do that, and then poach. (I assume you are poaching in some kind of infused syrup.) ;o)
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