Melt the Butter & Chocolate – In a saucepan over low heat, melt the butter and chopped bittersweet chocolate, stirring until smooth. Remove from heat and let cool slightly.
Mix Wet Ingredients – In a large bowl, whisk together the granulated sugar, brown sugar, eggs, vanilla extract, and sourdough starter. Stir in the melted chocolate mixture.
Combine Dry Ingredients – In a separate bowl, whisk together flour, cocoa powder, salt, and espresso powder.
Fold Everything Together – Gently fold the dry ingredients into the wet ingredients until just combined. Stir in chocolate chips if using.
Ferment (Optional) – If using active sourdough starter, cover the batter and let it ferment at room temperature for 4-12 hours for deeper flavor. If using discard, bake immediately.
Bake – Preheat oven to 350°F (177°C). Pour batter into a 9x9-inch lined baking pan and bake for 30-35 minutes, or until a toothpick inserted in the center comes out with a few moist crumbs.
Cool & Serve – Let brownies cool in the pan for at least 30 minutes before slicing. Enjoy!