Recently, interest in technology for eco-friendly energy harvesting has been increasing. Polyvinylidene fluoride (PVDF) is one of the most fascinating materials that has been used in energy harvesting technology as well as micro-filters by utilizing an electrostatic effect. To enhance the performance of the electrostatic effect-based nanogenerator, most studies have focused on enlarging the contact surface area of the pair of materials with different triboelectric series. For this reason, one-dimensional nanofibers have been widely used recently. In order to realize practical energy-harvesting applications, PVDF nanofibers are modified by enlarging their contact surface area, modulating the microstructure of the surface, and maximizing the fraction of the β-phase by incorporating additives or forming composites with inorganic nanoparticles. Among them, nanocomposite structures incorporating various nanoparticles have been widely investigated to increase the β-phase through strong hydrogen bonding or ion-dipole interactions with -CF2/CH2- of PVDF as well as to enhance the mechanical strength. In this study, we report the recent advances in the nanocomposite structure of PVDF nanofibers and inorganic nanopowders.