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Herein, polyvinyl alcohol nanofibrous membrane was fabricated firstly by the high-curvature solid-needle electrospinning. The influence of electrode curvature (needle angle), spinning voltage, solution concentration and collector distance on nanofiber morphology was systematically investigated numerically and experimentally. Numerical simulation shows that the electrical field increases with the increase of spinning voltage, while decreases with the increase of needle angle and collector distance. The experimental results are consistent with the numerical results. Furthermore, the solution concentration can be used to adjust the diameter of polyvinyl alcohol nanofibers. The possible applications of the nanofiber membrane to energy generation, water treatment, and separation are also discussed. [ABSTRACT FROM AUTHOR]