Preheat a grill to medium high. Combine the beans, celery, red onion, vinegar, 1/4 teaspoon salt and a few grinds of pepper in a medium bowl; set aside.
Drizzle the cut sides of the escarole with 1 tablespoon olive oil and season with salt and pepper. Season both sides of the pork chops with salt, pepper and the chopped rosemary.
Lightly oil the grill grates. Arrange the escarole and pork on the grill. Grill the escarole until charred in spots and wilted, 1 to 2 minutes per side. Grill the pork until well marked and just cooked through, 4 to 5 minutes per side. Transfer to a baking sheet.
Divide the pork and escarole among plates and drizzle with any juices from the baking sheet. Toss the bean mixture with the remaining 2 tablespoons olive oil, season with salt and pepper and spoon over the escarole.