Melt the chocolate on low heat over the stovetop, stirring constantly, until completely smooth. Pour over popcorn and toss gently to coat. Be sure to stir up from the bottom because that's where the chocolate will settle.
Make the peanut butter drizzle next. In a pan over the stove top on low heat, stir together peanut butter, vanilla, powdered sugar, milk, and brown sugar. Stir well and allow mixture to warm through, but NOT boil.
Spread chocolate popcorn out on a parchment paper-lined cookie sheet. Drizzle peanut butter mixture over the popcorn, then sprinkle with mini chocolate chips and peanuts. Let sit in the refrigerator until set. Break up popcorn into chunks and serve.