This research focuses on fabricating a one-step nano-generator based on electrospun nanofibrous materials for wearable electronics textiles applications. A nanofibrous structure from Poly (vinylidene fluoride), PVDF, was produced using electrospinning technique. Performances of these structures were evaluated by using X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM). Piezoelectric properties of fabricated composites also were evaluated on a self-made system as a function of frequency. Results showed that not only electrospinning process can effectively improve piezoelectric properties of nanofiber mats by changing the crystalline structure (e.g. create the beta-phase) compared to PVDF film samples, but also the fibrous structure of these materials interestingly can be used in the wearable electronic textiles. By using a novel approach to fabricate the nanofiber layer along with incorporating the electrodes within the structure of the device, the electrical output was improved as high as 1 volt. These results imply promising applications for various wearable self-powered electrical devices and systems.