Herein, we report an innovative production of BiVO4/ZnO nanocomposites with various compositions of BiVO4 (0-20) wt % for successful alleviation of rhodamine B dye as cationic pollutant model. The promising direction for generation of ZnO nanoparticles was achieved by sol-gel route using triton-X-100 as templating agent. On the other hand, BiVO4 nanoparticles were introduced on ZnO surface using chemical route. X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), x-ray photoelectron spectroscopy (XPS), high resolution transmitted electron microscopy (HR-TEM), Brunauer-Emmett-Teller (BET) N2-adsorption-desorption isotherms and diffuse reflectance spectroscopy (DRS) analysis were employed to elaborate the nanostructure, chemical compositions, oxidation state, pore structure and optical tendency of the solid specimens. The experimental results manifest the generation of bismuth vanadate with strong chemical affinity to ZnO surface. The incorporation of bismuth vanadate surface depresses the band gap energy of ZnO and controls the rate of recombination of the massive charge carriers. Anchoring 15 wt % of BiVO4 on ZnO surface decomposes 90.8 % of RhB dye which attributes to the positive role of BiVO4 in reducing the rate of charge carrier recombination. Positive holes and OH. radicals are predominant species for the degradation process. The strikingly new nanocomposite is considered a promising photocatalyst for alleviation of organic pollutants from wastewater.