Preheat oven to 350ºF.
Line an 8×8-inch square baking pan with parchment paper, allowing excess to overhang pan edges. Set aside.
In a large bowl, whisk together the cocoa powder, espresso powder (if using), and boiling water until smooth.
⅓ cup unsweetened cocoa powder, 1 ½ teaspoons espresso powder, ⅔ cup boiling water
Add ⅓ cup chocolate chips and whisk until chocolate is melted.
⅓ cup semi-sweet chocolate chips
Whisk in melted butter and oil. (Mixture may look curdled.)
4 tablespoons unsalted butter, ⅔ cup vegetable oil
Add eggs, egg yolks, and vanilla and continue to whisk until smooth.
2 large eggs, 2 large egg yolks, 1 tablespoon vanilla extract
Whisk in sugar until fully incorporated.
2 cups granulated sugar
Add flour and salt and mix with rubber spatula until combined.
1 ¾ cups all-purpose flour, ¾ teaspoon kosher salt
Fold in remaining 1 cup chocolate chips.
1 cup semi-sweet chocolate chips
Scrape batter into the prepared pan and bake until a toothpick inserted in the center comes out with just a few moist crumbs attached, 50-60 minutes. Transfer pan to wire rack and cool 1 hour.
Using parchment overhang, lift brownies from the pan. Return brownies to the wire rack and let cool completely, about 1 hour. Cut into 16 squares and serve.