In the present context, there is a global interest for developing low-cost, sustainable energy harvesting technologies to solve the global energy crisis due to overconsumption and depletion of fossil fuels. The study is intended to fabricate a novel nanogenerator based on polymer nanocomposite(polyvinylidene fluoride (PVDF) as a matrix) utilizing silanized multi-wall nanotubes (MWNT’s) with 3-aminopropyl triethoxysilane (APTES). The piezoelectric properties of the PVDF-MWNTs were systematically investigated by varying concentrations of CNT, CNT-APTES, and PVDF and its effect on the output voltage. Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD) to quantify the β-fraction and Differential Scanning Calorimeter (DSC) were performed to understand the crystallization behavior of PVDF matrix with hybrid silanized MWNTs. FTIR, XRD results indicate beta-phase enhancement in the PVDF matrix which aids in obtaining piezoelectricity. Further, morphological studies of the nanocomposites were done using Scanning Electronic Microscopy (SEM) and Transmission Electron Microscopy (TEM) to identify the fiber dimensions and state of dispersion of nanoparticles. The fabricated nanogenerator exhibited a voltage of 2 V which can be used to charge mobile phone and power a LED. Further, polymeric piezoelectric nanogenerator devices fabricated have great potential in solving the world-wide energy crisis in upcoming decades.