Season chops on both sides with salt and pepper. Heat 2 tablespoons of olive oil in a large skillet over medium-high heat until hot. Add pork chops; sauté for 5 minutes per side or until nicely browned on the outsides and cooked through.
Meanwhile, add remaining 2 tablespoons of olive oil to a large saucepan over medium heat. While the saucepan is still cool, add the garlic and crushed red pepper flakes; cook until garlic has browned, but not burned!
Remove the garlic and add the chard; toss with tongs to coat with the garlic oil then season with salt and pepper and cook until wilted.
Add the vinegar and give the chard one good toss before serving alongside the pork chops.