Besides the obvious cardinal importance of chemistry, every great romantic comedy film has to have one other element that rises it above the usual formulaic and terrible contenders that try all call themselves romantic comedies. That #2 element is "layers." If your romantic comedy main characters are caricatures or one-dimensional archetypes, then your audience won't identify with them, fall for them, or root for them. You've got to have something more than chemistry and two pretty faces. That's where the layers come in.
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