A poly(vinylidene fluoride) film and nanofiber were fabricated from a mixed solvent of N,N-dimethylformamide and non-polar acetone. With increasing acetone content in the mixed solvent, the viscosity of the PVDF solution decreased and the evaporation of the solution during electrospinning process was promoted. X-ray diffraction and infrared spectroscopy were used to examine the effect of the volatilization rate of mixed solvent on the nucleation rate of the PVDF crystal phases. With increasing acetone content in the poly(vinylidene fluoride) polymer solution, the rate of a-nucleation decreased with rapid volatilization of the solvent.