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Preheat oven to 350°F (175°C) and lightly grease a 6" cast iron skillet with butter.
Mix melted butter (slightly cooled) with both sugars until smooth.
Stir in egg yolk and vanilla until smooth.
In a separate bowl, whisk together flour, cocoa powder, baking soda, and salt.
Fold the dry ingredients into the wet until just combined.
Gently fold in chocolate chips.
Press most of the dough evenly into the skillet and add the marshmallows.
Add the rest of the dough on top and around the marshmallows, ensuring they are held in place by the dough.
Bake 13-16 minutes until center is mostly set but still soft.
Let rest 5-10 minutes before adding vanilla ice cream and other toppings.
Serve while gooey and enjoy!