Prepare the pan. Preheat the oven to 350°F, then lightly grease a 9×9 square baking pan with parchment paper.
Line the bottom of the pan with a single layer of graham crackers, breaking them as needed to fit, then set aside.
Make the brownie batter. In a large bowl, sift together the flour, cocoa powder, and salt. Set aside.
In a microwave-safe bowl, heat the butter in 30 second increments until melted and very hot (be careful not to let the butter pop or explode).
Add the granulated sugar to the butter, whisking until well incorporated and very smooth, around 2 minutes.
Crack in the eggs one at a time followed by the egg yolk, then add the vanilla extract. Whisk the mixture until smooth and lightened slightly in color.
In a separate small bowl, heat the chocolate in the microwave or over a double boiler, stirring every 30 seconds until melted. Allow the chocolate to cool slightly before adding to the egg and sugar mixture. Whisk well until homogeneous.
Using a rubber spatula, fold in the dry ingredients until just combined and no streaks of flour remain, then pour the brownie batter over the graham crackers in the prepared pan.
Bake for 35-40 minutes, or until the brownies are puffed and set in the middle; if you insert a toothpick into the center of the pan, a few moist crumbs should stick to it, but not raw batter (the brownies will continue to cook and set as they cool).
Remove the brownies from the oven and allow to cool. Once completely cooled, lift the brownies out of the pan and onto a cooling rack.
Decorate. To make the spiderweb decoration, place the marshmallows into a heat-safe bowl and microwave for 20-30 seconds or until melted. Stir until smooth.
Once cool enough to handle, use your fingers to stretch the marshmallows apart to create a spiderweb effect. Drape the marshmallow web over the top of the brownies and gently press to adhere.
Repeat until the top of the brownies are covered in webs. When ready to serve, use a sharp knife to slice the brownies into even pieces, running the blade under hot water and wiping it off in between cuts.
Store any leftover brownies in an airtight container for up to 4-5 days at room temperature.