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 Chef Rick Bayless prefers to roast large fresh chiles like poblanos over a charcoal or wood fire because he thinks that’s the way they taste the best. We’ll admit it’s impractical, however, in January in Chicago. Our second choice is to roast them over the flame of a gas burner. Third choice is to roast them close up under a very hot broiler. With this method, the flesh of the chile tends to cook more than we like before the skin blisters, because most home broilers aren’t nearly as hot as the grill or the flame.
The reason we roast chiles at all is to cook the flesh a little (cooked chile tastes less grassy), to rid them of their tough skins and to add a touch of smokiness. Large fresh chiles require a bit of vigilance during the roasting process: you want to evenly char—really char—the skin without turning the flesh to mush. That means a very hot fire and frequent turning.
Many cooks tell you to put roasted chiles in a plastic bag and let them cool before peeling. Trapping all that heat means almost certain overcooking, so Rick recommends putting them in a bowl and covering them with a towel for a few minutes. The steam they release will loosen the skin, making them easier to peel.
 Most small chiles, like serranos and jalapeños, are roasted directly on a dry skillet or griddle (or on a grill or in the fire, if those are options) turning them until they’re soft and irregularly charred. Small chiles are rarely peeled after roasting.
Don’t hestitate to roast (and peel) fresh chiles a day or two ahead; they keep well in the refrigerator. Lots of cooks, especially in the Southwest where large chiles are grown, like to roast a lot of chiles at once and freeze them; the practice in vogue seems to be freezing the roasted chiles with the skins on; peeling them when defrosted seems to preserve flavor and texture.
Exerpt from Rick Bayless's Mexican Kitchen
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