The electrospun PVDF has gained much attentions due to its excellent piezoelectricity, high flexibility, and low-cost. This study aims to develop the electrospun PVDF nanofibers with high β-phase concentration and piezoelectricity. The samples were prepared by the PVDF solution with different molecular weights. The earth abundant Zinc Oxide nanoparticles serve as the inorganic dopant to increase the polarization of the PVDF film during manufacturing process. The materials characterization methods, including Scanning Electron Microscopy, Energy Dispersive X-Ray, and Fourier-transform infrared spectroscopy were utilized to identify the material properties. The results indicate that the high molecular weight PVDF is favorable for electrospinning to obtain the high quality nanofibers. Furthermore, doping Zinc Oxide nanoparticles can effectively promote the polarization of electrospun PVDF nanofibers.