Preheat oven to 325 degrees F (165 degrees C). Spray a baking dish with cooking spray. Spread 1/2 of the pesto over into the bottom of the baking dish.
Heat a cast iron skillet over medium-high heat for 5 minutes. Add olive oil.
Season pork chops with salt and pepper. Cook pork chops in the hot oil until browned, about 4 minutes per side. Transfer pork chops to baking dish and top each with remaining pesto. Season with red pepper flakes. Cover baking dish with aluminum foil.
Bake in the preheated oven until an instant-read thermometer inserted into the center should read at least 145 degrees F (63 degrees C), about 1 1/2 hours. Allow pork chops to rest for 10 minutes.