In this work, we report the superior piezoelectric energy harvester ability of a non-electrically poled Fe-doped reduced graphene oxide (Fe-RGO)/poly(vinylidene fluoride) (PVDF) nanocomposite film prepared through a simple solution casting technique that favors the nucleation and stabilization of ≈99% relative proportion of polar γ-phase. The piezoelectric energy harvester was made with non-electrically poled Fe-RGO/PVDF nanocomposite film that gives an open circuit output voltage and short circuit current up to 5.1 V and 0.254 μA by repetitive human finger imparting. The improvement of the output performance is influenced by the generation of the electroactive polar γ-phase in the PVDF, due to the electrostatic interactions among the –CH₂–/–CF₂– dipoles of PVDF and the delocalized π-electrons and remaining oxygen functionalities of Fe-doped RGO via ion-dipole and/or hydrogen bonding interactions. Fourier transform infrared spectroscopy (FT-IR) confirmed the nucleation of the polar γ-phase of PVDF by electrostatic interactions and Raman spectroscopy also supported the molecular interactions between the dipoles of PVDF and the Fe-doped RGO nanosheets. In addition, the nanocomposite shows a higher electrical energy density of ≈0.84 J cm⁻³ at an electric field of 537 kV cm⁻¹, which indicates that it is appropriate for energy storage capabilities. Moreover, the surface of the prepared nanocomposite film is electrically conducting and shows an electrical conductivity of ≈3.30 × 10⁻³ S cm⁻¹ at 2 wt% loading of Fe-RGO.