Heat the olive oil in a large skillet over medium-high heat. Season the chuck roast with salt, black pepper, garlic powder, onion powder, oregano, basil, and red pepper flakes. Sear the roast in the skillet for about 4-5 minutes on each side until browned.

Transfer the seared roast to the slow cooker. Add the beef broth, pepperoncini peppers with juice, sliced onion, and sliced bell pepper on top of the roast.

Cover and cook on low for 8 hours or high for 4 hours, until the beef is tender and easily shredded.

Once cooked, remove the roast from the slow cooker and shred it using two forks. Return the shredded beef to the slow cooker and stir to combine with the juices and vegetables.

To serve, scoop the beef mixture onto hoagie rolls and top with provolone cheese if desired. You can toast the rolls under the broiler for a few minutes for extra crunch.