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Spray insert of 6- to 7-quart slow cooker with cooking spray. Open and separate the refrigerated biscuits into 8 biscuits.
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Cut each biscuit into 6 pieces; place in large bowl.
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Cut 1 cup pepperoni slices into quarters. Place half of the quarters in bowl with biscuit pieces. Add 3 teaspoons Italian seasoning to bowl with cut biscuits and pepperoni quarters; toss to mix.
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Place biscuit mixture as evenly as possible in bottom of slow-cooker insert.
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Spread the pizza sauce evenly over top of biscuits, making sure to get some sauce around edges so that biscuits are not touching insert without sauce in between.
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Sprinkle the shredded mozzarella cheese and remaining half of pepperoni over top, trying to keep cheese away from touching insert.
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Cover top of insert with large paper towel. Place slow-cooker lid on top of paper towel. (This will prevent condensation from dripping onto biscuits during cooking.)
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Cook on High heat setting 1 hour 30 minutes to 2 hour. (Not all slow cookers cook the same. Test for doneness after 1 hour and 30 minutes by inserting knife into center to make sure biscuits are fully baked; outer edge will be dark golden brown.)
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Remove bubble-up bake from slow-cooker insert while warm to prevent biscuits from sticking to insert.
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Serve warm