Adjust the oven rack to the lowest position and preheat the oven to 350 degrees Fahrenheit.
Spray a 9×13-inch pan with non-stick cooking spray, then line with parchment paper, leaving about a one-inch overhang on the sides.
Prepare the Peanut Butter Filling: Melt the creamy peanut butter and unsalted butter together in a medium bowl in the microwave until completely melted and smooth, about 1 to 2 minutes, stirring occasionally.
Whisk in the vanilla extract, then gradually whisk in the powdered sugar until completely smooth. Set aside while you prepare the brownie batter.
In a large bowl, whisk the cocoa powder and boiling water together until smooth.
Add the unsweetened chocolate and whisk until melted.
Whisk in the melted butter and oil until combined.
Add the eggs, yolks, and vanilla extract, whisking until smooth and homogeneous.
Whisk in the granulated sugar until fully incorporated.
Add the flour and salt, mixing with a rubber spatula until just combined.
Gently fold in the chocolate chips, if using.
Pour half of the batter into the prepared pan, spreading it into an even layer.
Turn the peanut butter filling out onto a clean work surface and press into a rough rectangle.
Transfer that filling onto the brownie batter in the pan.
Pour the remaining batter over the peanut butter filling and spread it evenly.
Bake until a toothpick inserted comes out with just a few moist crumbs, about 28 to 35 minutes.
Transfer the pan to a wire rack and cool for 1½ hours.
Using the parchment overhang, lift the brownies from the pan and cool completely on a wire rack for about 1 additional hour.
Cut into squares and serve. Store in an airtight container at room temperature for about 4 days.