Polyvinylidene difluoride (PVDF) fibers were prepared by electrospinning from dimethyl formamide (DMF) solutions. The effects of the electrospinning processing conditions on the formation of the alpha and beta phases of PVDF were studied using infrared spectroscopy and differential scanning calorimetry. We have shown that beta-phase PVDF fibers can be electrospun directly from a dimethyl formamide (DMF) solution with a maximum fraction of beta phase, F(beta)(max), of 0.75. The fraction of beta phase is found to be greater for smaller-diameter fibers and those spun at an increased voltage.