To roast a pepper, start with a hot fire and whole, washed peppers. Place them over the fire, turning frequently, until they are charred and blistered on the outside. They won't look to edible but the black stuffs coming off in a minute. Take the peppers or chilies from the fire and place immediately in a paper or plastic bag. Close the bag and let them sit for about 10 minutes. The heat from the grill and the moisture from the pepper will sweat the skin loose. After the ten minutes are up, remove the peppers from the bag and scrap the black off with a kitchen knife. It will be messy, but the skin should come off easily. Once the skin is cleaned off, cut the pepper open, remove the stem and the seeds from the inside and you're done.
Of course it's important to remember that peppers can be hot and roasting them can release the capsaicin (the stuff that makes hot foods hot) and so be careful handling them. In fact, be careful roasting them as well. Roasting peppers can release capsaicin into the air while cooking. Use rubber gloves or be sure to wash your hands thoroughly after you have handled the chilies. It is also important to use fresh roasted peppers and chilies soon. They can be stored in the refrigerator for a day or two, but they are best freshly roasted. Also, washing the peppers after you have scraped of the skin will cause them to lose some of their flavor, so if you want to hold on to the heat, keep them away from the water.
Fresh fire roasted peppers and chilies can be substituted in any recipe that calls for peppers. The addition of the smoky flavor will add to most any recipe. They also make a great appetizer or the base for a fresh salsa, so try roasting up some peppers next time your in the mood for a flavor with bite.