In a large pot over medium heat, bring 3 quarts of heavily salted water to a rolling boil. Have a large bowl of ice water ready on the side.
Add the broccolini and cook for 2 to 3 minutes, depending on the size of the broccolini. Quickly drain the water and place the broccolini in the ice bath to stop the cooking process. When the broccolini is cool remove them from the ice bath and place on a paper towel- lined plate.
Preheat the pizza oven OR regular oven to broil with a rack set in the top third of the oven. In a medium bowl toss the broccolini in olive oil, shallot garlic to coat then arrange in a single even layer on a baking sheet.
Sprinkle it with red pepper flakes and sea salt. Broil until the tips of the broccolini start to char but are not burnt, about 5 to 6 minutes. Remove from the broiler and place back in the bowl. Add the red wine vinegar and chili oil and serve.