Influence of temperature on morphology, structure and crystallinity of Poly (vinylidene fluoride) (PVDF) nanofibers was investigated in this study. The Wehilmy technique and viscosity testing apparatus were used to evaluate the surface tension and viscosity of electrospun solutions at various ambient temperatures. Surface morphologies and diameters of nanofibers were examined by Field-emission Scanning Electron Microscopy (FE-SEM) and atomic force microscopy (AFM). It was found that the surface morphologies were obviously affected by ambient temperature. This dependence was attributed to the change of the properties of Poly (vinylidence fluoride) solutions with temperature. The thermal properties and crystal structures of the PVDF nanofibers electrospun at different temperatures were also studied by differential scanning calorimetry (DSC), and Xray diffraction (XRD). The results revealed that the crystallinity and thermal properties were improved by increasing the ambient temperature during electrospinning.