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Preheat oven to 500˚F. Place whole bell peppers on a rimmed baking sheet lined with foil and roast 30-40 min until skins are completely wrinkled and peppers are charred, turning a couple times while roasting. Remove from oven, cover tightly with aluminum foil and let rest 30 min until cool enough to handle.
Remove stems and cut the bell pepper into quarters. Remove and discard peels and seeds. Slice peppers into 1/2” wide slices and transfer to a medium bowl.
Add 1 1/2 Tbsp olive oil, 2 tsp balsamic vinegar, 2 pressed garlic cloves, 1 tsp sea salt and 1/2 tsp black pepper. Stir to combine, cover and refrigerate 1 hour (or overnight) for the flavors to meld.
Brush both sides with olive oil and bake at 350˚F for 5 minutes, just until edges are crisp and centers are still soft. Remove form oven and cool to room temperature.
Spread a thin layer of goat cheese over the top of toasts then divide the marinated roasted peppers evenly between 25 toasts and garnish with fresh basil.