Herein, we report the synthesis of poly (vinylidene fluoride) (PVDF) based novel nanocomposites reinforced with graphene nanoplatelets (GNP) and vanadium pentoxide (V2O5) as nanofillers. The PVDF/V2O5/GNP nanocomposite films were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), thermogravimetric analysis (TGA), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The electrical properties of nanocomposites were investigated to ascertain the synergistic effect of fillers on the quality factor (Q-factor) of nanocomposites. The FTIR and XRD results infer good interaction between PVDF and V2O5 and the good dispersion of nanofillers in the PVDF matrix. The TGA results revealed that the thermal stability of PVDF/V2O5/GNP nanocomposite has improved at higher loading of nanofillers due to the good interaction between the nanofillers and the polymer matrix. The electrical analysis of nanocomposite films demonstrates high Q-factor value (1099.04) at 4.7 wt % V2O5 and 0.3 wt % GNP loading. With further increase in GNP loading to 1 wt %, the Q-factor becomes lower (356.52) which could be due to the enhanced conductivity of the samples. The significant enhancement in the value of Q-factor shows that the nanocomposites can be used as a potential candidate for high-Q capacitor applications.