The characteristics of poly(vinylidene fluoride) (PVDF) nanofibers, prepared by applying the electrospinning technique from N,N-dimethylformamide/acetone mixtures, were studied by varying the experimental conditions. The nanofiber morphology was assessed by scanning electron microscopy, while wide angle X-ray diffraction and infrared spectroscopy were performed to study the crystallinity. The influence of the electrospinning conditions, such as kind of solvent mixture, polymer concentration, voltage tension, airflow and humidity, on nanofiber morphology was studied. In particular, the latter parameter, generally not considered, was found to modify the electrospun mat structure in a relevant way. Generally, the above technique turns out to be capable of strongly affecting the polymorphism of the polymer, namely beta phase formation was higher in the electrospun mats compared with cast films, which displayed a non-polar alpha crystal phase. As far as the influence of the electrospinning conditions on PVDF crystal structure is concerned, modification of the experimental parameters did not affect the alpha/beta ratio. Nevertheless, comparing the behavior of two commercial PVDF samples with similar molecular masses, our results show that the polymer which forms a higher content of beta phase in its cast films allowed electrospun mats characterized by almost complete formation of beta phase to be obtained. (C) 2012 Society of Chemical Industry