ZnO-based heterojunctions have found applications as self-powered ultraviolet photodetectors (PDs). However, high doping levels are not compatible with high mobility for metallic doped ZnO-based PDs so further development has been inhibited. This study demonstrates a method to increase the open-circuit voltage (V ) that allows keeping a sufficiently high level of mobility of ZnO, using a ZnO nanorod/GaN heterojunction that incorporates graphene nanosheets as the active layer. These hybrid PDs have triple the value for V of PDs that have only pure ZnO and better exhibit photo-response characteristics. The results of surface Kelvin probe microscopy and x-ray photoelectron spectrometer show that the complex defects that occur because Zn interstitials form a shallow donor in ZnO are mainly responsible for the increase in the value of V . Using this functional nanostructure as an active layer represents a new method for the manufacture of high-performance self-powered PDs.