The polymorphism and crystallinity of poly(vinylidene fluoride) (PVDF) membranes, made from electrospinning of the PVDF in pure N,N-dimethylformamide (DMF) and DMF/acetone mixture solutions are studied. Influence of the processing and solution parameters such as flow rate, applied voltage, solvent system, and mixture ratio, on nanofiber morphology, total crystallinity, and crystal phase content of the nanofibers are investigated using scanning electron microscopy, wide-angle X-ray scattering, differential scanning calorimetric, and Fourier transform infrared spectroscopy. The results show that solutions of 20% w/w PVDF in two solvent systems of DMF and DMF/acetone (with volume ratios of 3/1 and 1/1) are electrospinnable; however, using DMF/acetone volume ratio of 1/3 led to blockage of the needle and spinning process was stopped. Very high fraction of b-phase (79%-85%) was obtained for investigated nanofiber, while degree of crystallinity increased to 59% which is quite high due to the strong influence of electrospinning on ordering the microstructure. Interestingly, ultrafine fibers with the diameter of 12 and 15 nm were obtained in this work. Uniform and bead free nanofiber was formed when a certain amount of acetone was added in to the electrospinning solution.