Nanocrystalline core/shell structures of cetytrimethylammonium bromide (CTAB)-assisted ZrO2, V2O5, and ZrO2V2O5 composite was successfully prepared by co-precipitation method calcined at 500 degrees C. CTAB-assisted ZrO2, V2O5, and ZrO2-V2O5 composite were characterized by different techniques such as, X-ray diffraction (XRD), Fourier Transform Infrared (FT-IR), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Brunauer-Emmett-Teller (BET), Ultra-Violet (UV) and Photoluminescence (PL). The formation of ZrO2, V2O5, and ZrO2-V2O5 composite material has been confirmed by XRD studies. Surface morphology with grain size of CTAB-assisted ZrO2, V2O5, and ZrO2-V2O5 composite was determined by SEM and TEM studies. EDX analysis confirms the presence of compositional elements of ZrO2-V2O5 composites in the lattice such as zirconium, vanadium and oxygen. Optical studies reveal a strong absorption and emission peaks were presented in the UV and visible regions and it useful for optoelectronic device applications. In comparison, ZrO2, V2O5, and ZrO2V2O5 composite exhibited the higher band gap energies with a significant blue-shift and enhanced UV light absorption compared to bulk counterparts. As-prepared photocatalysts, CTAB-assisted ZrO2, V2O5, and ZrO2V2O5 composite showed strong photocatalytic activity towards the degradation of Rhodamine B (RhB) dye under UV light irradiation, which can facilitate the efficient separation and migration of photo generated electron-hole pairs. Among result, the ZrO2-V2O5 composite exhibited the synergistic enhanced photocatalytic performance and also the possible photocatalytic mechanism was discussed in detail.