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Intrinsic electrical and excitonic properties of monolayer transition‐metal dichalcogenides can be revealed on CYTOP fluoropolymer substrates with greatly suppressed unintentional doping and dielectric screening. Ambipolar transport behavior is observed in monolayer WS2 by applying solid‐state back gates. The excitonic properties of monolayer MoS2 and WS2 are determined by intricate interplays between the bandgap renormalization, Pauli blocking, and carrier screening against carrier doping.