W18O49 nanostructures, previously used for electrocatalysis, energy storage, electrochromic, and gas sensing applications, are incorporated in poly(vinylidene fluoride) (PVDF) in this work for mechanical energy-harvesting applications. X-ray diffraction spectroscopy (XRD), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, differential scanning calorimetry (DSC), and the polarization-electric (P-E) field loop test prompts the addition of W18O49 nanorods in PVDF nucleates and stabilizes the piezoelectric polar γ-phase in the nanocomposite. Electrochemical experiments were employed for the first time to relate the event of the evolution of crystalline phases in PVDF to the transfer of electrons to the electrolyte from PVDF using the data from cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). High dielectric constant (ε') and low dielectric loss (ε″) values were obtained proportionately for different weight percentage additions of W18O49 nanorods in PVDF. DSC was employed to study the crystallization kinetics of γ-phase evolution. Piezoresponse force microscopy (PFM) was used to compare the piezoelectric responses from the PVDF nanocomposites. The W18O49/PVDF nanocomposite could generate a peak open circuit voltage of ∼6 V and a peak short circuit current of ∼700 nA. The W18O49/PVDF nanocomposite could light two commercial blue-light-emitting diodes (LEDs) with hand impulse imparting.