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Lightly grease a 9-by-13-inch baking pan with cooking spray; set aside.
In a minimum 3-quart saucepan or Dutch oven, heat corn syrup and sugar over medium heat, whisking occasionally, until mixture is just bubbling around the edges, about 2 minutes.
Slowly whisk in peanut butter, vanilla, and kosher salt until peanut butter is completely incorporated and mixture is smooth, about 30 more seconds.
Off heat, fold in rice cereal with a rubber spatula. Transfer mixture to the greased pan and pat gently into place (do not overpack).
In a heatproof bowl, melt chocolate and butterscotch chips in microwave in 15-30 second intervals, stirring thoroughly between each interval, until glossy and smooth.
Pour over cereal and use rubber spatula to spread topping across the bars in a thin, even layer.
Sprinkle flaky salt over topping, if desired.
Let scotcheroos rest at room temperature for at least 2 hours or until topping is firm and set.
Cut into roughly 2-inch squares and serve.