Rinse neck bones and pat dry.
Season neck bones with salt, pepper, smoked paprika, garlic powder, onion powder, and cayenne.
Heat olive oil in a large pot over medium heat. Sear neck bones on all sides until browned.
Add onion, green bell pepper, and garlic. Sauté until fragrant.
Pour in chicken broth and add Worcestershire sauce and vinegar.
Bring to a boil, then reduce heat to low. Cover and simmer for 2.5 to 3 hours until meat is tender and falling off the bone.
Stir occasionally and add water if needed to maintain liquid level.
Serve hot over rice or mashed potatoes.