An enhanced photoinduced reversible switching of graphene oxide-azobenzene (GO-AZO) hybrid was investigated as a highly sensitive photoswitch. The internal short-range ordered crystalline structure of GO-AZO hybrid was advantageous to charge transfer. The AZO moieties on GO underwent a rapid trans-cis photoisomerization upon ultraviolet irradiation due to the electron interaction between AZO and GO. The GO-AZO hybrid film showed an enhanced reversible photoswitching performance with high on/off ratio of 8 and fast response time less than 500 ms. The high sensitivity or GO-AZO switch arises from the intramolecular donor-acceptor architecture with efficient charge transfer.