Set oven rack to middle position and heat oven to 350º F. Line an 8-inch baking pan with parchment paper, leaving the edges hanging over the side of the pan. Spray with cooking spray.
In a bowl, microwave chocolate and 8 Tbsp butter for 30 seconds. Stir and microwave for another 30 seconds. Stir and repeat until melted. Whisk in cocoa powder until smooth and set aside to cool.
For peanut butter swirl, combine melted butter, peanut butter, powdered sugar, salt and vanilla in a bowl and stir until smooth. Set aside.
In a large bowl, whisk the sugar, salt, vanilla, and eggs until combined. Whisk melted chocolate mixture into egg mixture. Stir in the flour until just combined. Do not over-mix. Pour mixture into the prepared pan. Drop dollops of peanut butter mixture on top of brownie batter. Use a butter knife to swirl in the peanut butter.
Bake until a toothpick inserted comes out mostly clean, about 35 - 45 minutes. Cool on a wire rack for 1 hour. Pull from pan using parchment paper liner. Cut into 2-inch squares when ready to serve.