Bring a large pot or Dutch oven to medium heat, and then add the onions, celery, and carrots.
Stir in the garlic, thyme, oregano, salt, and black pepper. Take 30 seconds to mix the spices with the vegetables.
Add the chopped tomato, tomato paste, vinegar, mustard powder, and cayenne pepper. Stir to distribute the ingredients, then add the barley and vegetable broth.
Bring the ingredients to a simmer, cover the pot and cook the barley for 20-25 minutes. Check periodically and add more liquid if needed.
Preheat the oven to 400 F (200 C).
There are two ways to prep the peppers. Cut the peppers half from stem to end. Or cut off the tops and use the pepper whole. Clean out the seeds and white membranes. Arrange the peppers on a baking tray lined with parchment paper or a large baking dish.
When the barley is cooked, remove it from the heat and mix in the white beans. Taste and adjust the flavorings.
Fill each pepper with spoonsful of the barley mixture. (If you have filling left over, it can be frozen). Arrange them back on the baking tray or dish.
Cover with aluminum foil and bake for 30 – 35 minutes or until the peppers are soft and tender.