In this study, the Poly(vinylidene fluoride-trifluoethylene) (PVDF) electrospun fibers were successfully prepared by electrospinning. Processing parameters, such as solvents and solution temperature were varied to study their influence on fiber dimensions. Electrospun PVDF fibers were characterized by scanning electron microscope (SEM), Fourier transform infrared spectrophotometer (FT-IR), wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The result indicated that the solvent component and temperature have great influence on fiber dimensions. 19% PVDF dissolved in DMF/MEK mixed solvents with the ratio of 8:2 was considered to be most suitable in this study. Furthermore, the increasing of solution temperature can probably induce the formation of beta-phases in electrospun PVDF Fibers.