Nanocomposite material ZnAl2O4/ZnO was prepared via layered double hydroxides co-precipitation method in the presence of triblock copolymer, Pluronic F127 as the template with different concentrations at pH 7. The material was characterized by XRD, N2 adsorption/desorption, UV–Vis diffused reflectance, TGA–DTA and SEM. XRD and SEM results reveal that ZnAl2O4/ZnO was highly ordered nanocrystalline material. N2 adsorption/desorption studies indicate that the pore size and pore volume increased significantly with the increase in concentration of F127 copolymer template, while the surface area is slightly decreased with increase of F127 template. TGA–DTA results reveal that the thermal stability of material increased after adding F127 template. The material was tested for its photocatalytic activity for a solution containing methyl orange dye and the 95.6% decolorization was achieved within 1 h. The intensive absorption light observed by UV–Vis reflectance of the catalyst confirmed high activity of the catalyst and suggest the probable photocatalytic degradation mechanism.