Line a 9x13 baking pan with parchment and spray gently with cooking spray. Measure out 6 cups of rice cereal into a large bowl.
Place the sugar and corn syrup in a medium pot over medium or medium low heat. Stir together and cook for a couple of minutes until the sugar crystals dissolve. As soon as the mixture comes to a boil with bubbles rolling across the center, remove it from the heat.
Immediately stir in the creamy peanut butter to make a glossy sauce.
Pour the peanut butter sauce over the cereal in a large bowl and stir to evenly combine.
Pour the cereal mixture into the prepared pan. Using a damp hand, gently press the mixture into the pan and smooth the top. Do not push the cereal down hard or the bars will be hard.
Place the chocolate chips and butterscotch chips in a microwave safe bowl and microwave 30 seconds at a time until melted, stirring thoroughly in between each time in the microwave. Pour the melted chocolate over the cereal mixture and use a knife or offset spatula to smooth it out.
All scotcharoos to set up at room temperature until chocolate is firm, 2-4 hours. You can place the bars in the fridge to help chill the chocolate (and may need to on a hot day). Just remove the bars from the fridge as soon as the chocolate is set and allow them to come back to room temperature before serving.
Use the parchment paper to pull the scotcharoos out of the 9x13 pan and place on a cutting board. Cut into pieces and serve. Store covered.