PVP/Zn(CH3COO)2/Fe(NO3)3 composite nanofibers were prepared, and by high temperature sintering of the above precursor fibers, ZnO-Fe3O4 composite nanofibers were successfully obtained. Field-emission scanning electron microscope (FE-SEM), energy dispersive spectroscopy (EDS), thermal gravimetric analysis (TG), fourier transform infrared spectroscopy(FT-IR) and X-ray diffraction(XRD) were used to characterize the nanofibers before and after sintering. The results show that the diameters and the crystallinity of the nanofibers are significantly influenced by sintering temperature. When sintering temperature ranges from 400 °C to 700 °C, the average diameter of nanofibers decreases with the increasing of sintering temperature. However, when up to 800°C, the average diameter of fibers increases slightly. X-ray diffraction spectra show that the crystallinity becomes better with the increasing of sintering temperature, and at 700°C, the crystallinity is best.