Preheat oven to 350 degrees F (175 degrees C). Grease an 8x8-inch baking pan.
Place 1/2 cup butter and white sugar in a microwave-safe bowl. Heat in microwave on high until butter is melted, about 1 minute. Stir 2 ounces baking chocolate into butter-sugar mixture until chocolate melts. Stir in eggs; mix well. Add flour, 1 tablespoon orange liqueur, vanilla extract, and salt; stir to combine. Pour batter into the prepared baking dish.
Bake in the preheated oven until the top is dry and the edges have started to pull away from the sides of the pan, 20 to 25 minutes. Remove from oven and cool completely.
Place remaining 1/4 cup butter in a large microwave-safe bowl. Heat in microwave on high until melted, about 30 seconds. Stir 1 ounce baking chocolate into melted butter until chocolate melts. Stir in orange liqueur and 1/2 cup confectioners' sugar. Crumble the cooled brownies into the mixture; stir to combine.
Form brownie mixture into 1-inch balls; arrange on a baking sheet. Refrigerate until firm, about 2 hours. Insert a lollipop stick into each brownie ball.
Melt chocolate coating and chocolate chips in the top of a double boiler over simmering water, stirring frequently and scraping down the sides with a rubber spatula to avoid scorching. Keep warm.
Dip each brownie pop into the chocolate coating, allowing excess chocolate to drip back into the saucepan. Transfer the coated brownie pops onto a baking sheet or set upright into a piece of craft foam. Allow coating to set, about 1 hour.
Substitute white chocolate coating for chocolate if you like. Decorate with sprinkles or your favorite topping.
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