The demands for wearable technologies continue to grow and novel approaches for powering these devices are being enabled by the advent of new energy materials and novel manufacturing strategies. In addition, decreasing the energy consumption of portable electronic devices has created a huge demand for the development of cost-effective and environment friendly alternate energy sources. Energy harvesting materials including piezoelectric polymer with its special properties make this demand possible. Herein, we develop a flexible and lightweight nanogenerator package based on polyvinyledene fluoride (PVDF)/LiCl electrospun nanofibers. The piezoelectric performance of the developed nanogenator is investigated to evaluate effect of the thickness of the as-spun mat on the output voltage using a vibration and impact test. It is found that the output voltage increases from 1.3 V to 5 V by adding LiCl as additive into the spinning solution compared with pure PVDF. The prepared PVDF/LiCl nanogenerator is able to generate voltage and current output of 3 V and 0.5 µA with a power density output of 0.3 µW cm−2 at the frequency of 200 Hz. It is found also that the developed nanogenerator can be utilized as a sensor to measure temperature changes from 30◦C to 90◦C under static pressure. The developed electrospun temperature sensor showed sensitivity of 0.16%/◦C under 100 Pa pressure and 0.06%/◦C under 220 Pa pressure. The obtained results suggested the developed energy harvesting textiles have promising applications for various wearable self-powered electrical devices and systems.