As a piezoelectric polymer, poly (vinylidene fluoride) (PVDF) is attractive in energy conversion applications between electrical and mechanical forms because of its low cost, high flexibility, and biocompatibility. The piezoelectricity of electrospun PVDF polymer is due to changes in the crystalline structure (e.g., creating the -phase) during the electrospinning process. This research focuses on two approaches for investigation of Phase formation: (1) addition of LiCl in different concentrations (0.001, 0.00133, 0.002, 0.004 wt%) as inorganic salt to the polymer solution, (2) increasing tension along the fiber axis by increasing the collector drum speed during the aligning process. 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). A one-step nano-generator and cost-effective package based on electrospun nanofibers was presented to measure output voltages as a performance factor. Results show that the addition of LiCl leads to Phase formation in the crystalline structure, decreasing fiber diameter to 65 nm, and increment in the work of rupture and piezoelectric output. Moreover, the results show that increasing collector drum speed causes the alignment of -crystallites along the fiber axis and subsequently no considerable effect on the formation of -phases and output voltage. POLYM. ENG. SCI., 56:61-70, 2016. (c) 2015 Society of Plastics Engineers