This recipe uses several preservation techniques: The peppers are salted and drained overnight, pickled, then partially dried, and “confited” in olive oil. Each step helps reduce the chance of spoilage, first by driving out moisture, then acidifying the peppers, and drying once more. Finally, submerging the peppers in olive oil protects them from oxidizing or growing molds that need air to survive. After all this, the peppers are still not considered shelf-stable by the USDA and must be refrigerated.
So why do it? Though these delectable chiles take multiple days to prepare, once the raw peppers are slit open and seeded, there is very little labor involved. More importantly, you get three wonderful ingredients from one batch of peppers: a briny, chile-infused vinegar (use as you would any hot sauce; it is especially good sprinkled on cooked greens); chile-infused olive oil (perfect for bread dipping or marinating vegetables and cheese); and tangy, moderately spicy chiles (superb for topping pizzas and pasta dishes). Try this procedure once and we are confident you will be doing it every year. As for peppers, we prefer them to be ripe, red, and moderately spicy, though green, yellow, or super-hot chiles will certainly work.
Wearing protective gloves, trim off any long stems and slit open lengthwise on one side:
Scoop out most of the seeds and white ribs. Pour into a medium heatproof bowl:
Press each chile into the salt, making sure each one is thoroughly coated on the inside. Place the chiles in a colander as you work. When all the chiles have been treated this way, toss the chiles with any remaining salt and place the colander over the bowl. Cover and let the chiles drain overnight.
In the morning, discard any liquid in the bowl. Transfer the chiles to the bowl, shaking off any loose seeds or salt. Bring to a boil in a medium saucepan:
Pour the hot vinegar into the bowl, submerging the chiles (if necessary, weight them down with a small plate). Once cool, cover and let the chiles steep overnight.
Preheat the oven to 190°F.
Drain the chiles through a fine-mesh sieve set over a bowl to catch the infused vinegar (reserve this vinegar for other uses; it can be stored in a bottle or jar at room temperature). Place a rack set over a baking sheet and lay the chiles on top in one layer, leaving a little space between them. Dry out the chiles in the oven until the skins begin to wrinkle, about 2 hours (do not let them get crispy).
When the chiles are cool enough to handle, tightly layer them in a small baking dish (to ensure that no oil spills, you can set the baking dish on a rimmed baking sheet). Increase the oven temperature to 200°F and pour over the chiles:
Be sure they are covered with oil (you may place a loaf pan or other ovenproof weight on top of them if necessary). Bake for 2 hours.
Let cool completely. Pack the chiles into a sterilized quart jar, cover with the olive oil, and store in the refrigerator indefinitely.
To use the chiles, fish them out of the oil with a clean fork, discard the green calyx where the stem used to be, and roughly chop. After being in the refrigerator for a while, olive oil solidifies and turns opaque. Simply scoop out the desired number of chiles with their oil into a small bowl and allow them to sit at room temperature until the oil liquefies.