Preheat the oven to 350 degrees F. Cut the potatoes into 1/2-inch cubes. Heat 1 tablespoon olive oil in a large cast-iron skillet over high heat, 3 minutes. Add the potatoes; cook, stirring, until tender and browned, 10 to 15 minutes.
Meanwhile, bring a pot of generously salted water to a boil. Add the broccoli rabe and cook until just tender, 3 to 4 minutes. Drain and transfer to a medium bowl. Add 1 tablespoon olive oil, the lemon zest and the chiles and their oil.
Season the pork chops with salt and pepper. Push the potatoes to the edge of the skillet, reduce the heat to medium high and add the remaining 1 tablespoon olive oil to the middle of the pan. Add the pork chops and cook until browned, about 2 minutes per side, turning the potatoes as needed. Transfer the skillet to the oven and bake until a thermometer inserted into the center of the pork registers 145 degrees F, 4 to 5 minutes. Transfer the pork chops to plates.
Season the potatoes with 1/2 teaspoon salt and stir to coat in the pan drippings. Serve the pork chops with the potatoes, broccoli rabe and lemon wedges.