Preheat oven to 350°F and line a 9x13-inch baking dish with parchment paper.
In a large bowl, whisk together cocoa powder, flour, baking powder, salt, and espresso powder. Set aside.
In a large saucepan over medium heat, melt butter and sugar. Bring to a low boil and cook for 2 minutes until it reaches 230°F, stirring occasionally.
Remove from heat and stir in chocolate chips and vanilla until melted, then let cool about 10 minutes.
Add eggs one at a time, stirring constantly until smooth.
Fold dry ingredients into chocolate mixture until just combined; batter will be thick.
Spread half the batter evenly into the lined baking dish.
Spread creamy peanut butter over the batter layer evenly.
Pipe marshmallow fluff over the peanut butter layer using a piping bag or plastic bag corner.
Top with remaining brownie batter and spread evenly.
Bake for 28 to 30 minutes until set.
Allow brownies to cool completely before cutting and serving.