Put the unopened bag of mini marshmallows in the freezer for 15–20 minutes as you organize the remaining ingredients and equipment. The chilled pieces will better retain their individual shapes when they meet the warm coating.
Fit parchment paper into a 9x13 baking pan. Covering the bottom and sides keeps the sticky mixture from clinging directly to the pan.
Stir the butter, butterscotch chips, and peanut butter together in a saucepan over medium-low heat, without allowing the mixture to boil. Stop heating once the butter has fully melted and the coating looks glossy, creamy, and free of lumps.
Empty the cold marshmallows into a large bowl, then cover them with the melted peanut butter and butterscotch coating. The coating should still flow easily around the marshmallow pieces.
Fold the mixture thoroughly to cover every marshmallow. Look for an even coating with no dry pockets hiding at the bottom of the bowl.
Transfer the coated marshmallows to the lined pan and use a rubber spatula to pat them into an even layer. A level surface and filled corners help the slab chill to a consistent thickness.
Refrigerate the filled pan for 1–2 hours. The coating should feel firm enough for the slab to hold its shape during slicing.
Divide the firm slab into 24 squares. The cut edges should stay upright rather than slump or smear.