Preheat oven to 400°.
Line a baking sheet with parchment paper. Arrange the peppers skin side down on the baking sheet and drizzle with 2 tbsp olive oil. Season with salt and pepper and roast until tender, about 20 minutes.
To make the toasted breadcrumbs, place the torn bread into a food processor and whirl for 1-2 minutes until completely broken down. Transfer the breadcrumbs into a large skillet and place over medium heat. Drizzle the bread crumbs with the remaining olive oil and saute until golden brown and crisp.
Transfer the bread crumbs back into the food processor, along with the chopped chives, basil and garlic and pulse for 1-2 minutes until everything is evenly incorporated.
Top the roasted peppers with the herbed bread crumbs and serve immediately.