In this work, a novel heterojunction based on ZnSnO3/ZnO nanofibers was prepared using electrospinning method. The crystal, structural and surface compositional properties of sample based on ZnSnO3 and ZnSnO3/ZnO composite nanofibers were investigated by X-ray diffractometer (XRD), Scanning electron microscope (SEM), X-ray photoelectron spectrometer (XPS) and Brunauer-Emmett-Teller (BET). Compared to pure ZnSnO3 nanofibers, the ZnSnO3/ZnO heterostructure nanofibers display high sensitivity and selectivity response with fast response towards ethanol gas at low operational temperature. The sensitivity response of sensor based on ZnSnO3/ZnO composite nanofibers were 19.6 towards 50 ppm ethanol gas at 225°C, which was about 1.5 times superior than that of pure ZnSnO3 nanofibers, which can be owed mainly to the presence of oxygen vacancies and the synergistic effect between ZnSnO3 and ZnO.