We report the first solar cell whose junction is formed by a polymer‐semiconductor interface. Open‐circuit voltages,Voc≳0.7 V, have been observed on cells consisting of a thin film of polymeric sulfur‐nitride, (SN)x, deposited on GaAs. This is an enhancement of more than 40% over theVoccommonly measured with metal‐GaAs solar cells. Initial efforts have resulted in efficiencies ≳6% without antireflection coatings.