Photoanode optimization is a fascinating technique for enlightening the power conversion efficiency (PCE) of dye-sensitized solar cells (DSSCs). In this present study, V2O5/ ZnO and reduced graphene oxide (rGO)-V2O5/ZnO nanocomposites (NCs) were prepared by the solid-state technique and used as photoanodes for DSSCs. A wet chemical technique was implemented to generate individual V2O5 and ZnO nanoparticles (NPs). The structural characteristics of the as-synthesized NCs were investigated and confirmed using powder X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), and Scanning electron microscope (SEM) with energy dispersive X-ray (EDX) analysis. The average crystallite size (D) of the as-synthesized V2O5/ ZnO and rGO-V2O5/ZnO NCs was determined by Debye-Scherer’s formula. The bandgap (eV) energy was calculated from Tauc’s plots, and the bonding nature and detection of the excitation of electrons were investigated using the Ultra violet (UV) visible spectra, Fourier Transform infrared (FTIR) and photoluminescence (PL) spectral analysis. Electrical studies like Hall effect analysis and the Nyquist plots are also described. The V2O5/ ZnO and rGO-V2O5/ZnO NCs based DSSCs exhibited 0.64% and 1.27% of PCE and the short circuit current densities and open circuit voltages improved from 7.10 to 11.28 mA/cm2 and from 0.57 to 0.68 V, respectively.