In this study, the optimum conditions for manufacturing PVDF nano web according to various electrospinning conditions such as solution concentration and applied voltage conditions were confirmed. The optimum spinning conditions were studied by analyzing the changes in the radioactivity of PVDF/TiO2 nano web according to the TiO2 content and the content of β-phase closely related to the piezoelectric properties under established conditions. As a result, it was confirmed that the concentration of the spinning solution was 20 wt%, the applied voltage was 25 kV, and the TiO2 content was 5 phr. PVDF nano web and PVDF/TiO2 nano web were observed morphologies through Scanning Electron Microscope(SEM) analysis. Formation of β-phase by electrospinning was confirmed by Fourier transform infrared spectroscopy(FT-IR) and X-ray Diffractometer(XRD), and the effect of the trapped nano web structure on the piezoelectric properties was investigated.