Depletion of fossil fuels and increase in pollution through chemical batteries trigger the development of self‐powered devices based on flexible piezoelectric nanogenerators. Biocompatible piezoelectric PVDF nanocomposites merged with piezoelectric fillers like ZnO, KNN, and BaTiO3 reproduce amended piezoelectric current, contributing to the safe application as biosensors and flexible industrial devices. Optimized loading, precise selection, and variating the surface chemistry of piezoelectric filler, along with fabrication schemes comprising different structural configurations of composites, considerably influence its potential for application as energy harvester. Also, optimized processing condition upgrades dielectric constant, energy storage density, and reduces dielectric loss, thereby plummeting energy dissipation even after prolonged usage. Consequently, this paper reviews the principles, properties, fabrication techniques, and market application of PVDF composites. A detailed relationship of significant electrical properties of PVDF composites with its fabrication methods and piezoelectric parameters of fabricated PVDF composites with reported real‐life wearable, implantable, and industrial‐based portable piezoelectric devices are discussed in detail along with tabulated data for clear understanding of structure‐property relationship. Again, market strategy for establishing flexible PVDF composite as a piezoelectric nanogenerator has been discussed. An in‐depth knowledge is provided for procuring affordable futuristic large‐scale PVDF‐based nanogenerators exhibiting affordable market worth.This article is protected by copyright. All rights reserved.