We always grow one or two chili pepper plants in our garden each year, and often end up with more peppers than I can use fresh. Some years I have made salsa, and hot peppers can also be frozen whole or sliced in half and seeded (just like sweet peppers). This year I wanted to try something different, so I fire roasted a bunch for a result that is smoky and a little sweet as well as spicy. I plan to use them in pots of chili, beans and rice, etc. through the winter. The technique is much like the technique for fire roasting sweet peppers (which I also recommend doing now that sweet peppers are fully in season).
You can use green or red chili peppers; the ripe ones will be a bit sweeter. If you have a mix of colors, I suggest keeping them them separate for strictly aesthetic reasons. I strongly suggest wearing gloves (regular rubber gloves are fine) while handling the chilies, especially when you are ready to peel them.
If you are using large chili peppers, you can cut them in half lengthwise and seed them before grilling. Otherwise, you put the whole peppers directly on the grill.
Get your grill going nice and hot. Lay the chili peppers out across the grate and grill, turning as needed, until the skin is blistered and they are black all over. Do not be shy about this, because the skin is very hard to remove if not fully blackened. However, keep and eye on the chilies because you also don't want to char them so fully that you burn the flesh under the skin.
When the chilies are fully blackened, remove them from the grill and set them in a bowl with something covering it (they will steam a little, which also helps loosen the skins) until they are cool enough to handle. Wearing gloves and using a paring knife, slice the top (stem part) off each chili and run the knife around the inside of it to remove as much of the seeds as possible. Then peel or scrape off the blackened skins. The chilies will get slippery as you peel them, so handle with care.
Once you have your peeled chilies, you can use them as is (probably mince first) and store them in the fridge. You can also puree them. I opted to puree and then tray freeze little dollops, stored in freezer bag for use in small quantities.