The surface of hexagonal ZnO was subjected to preliminary treatment with Ni2+ ions that transformed into a homogeneously coated layer by air calcination process in the loading range of 0.3–5 % with respect to the weight of ZnO support. The enhanced absorption in the visible region evidenced the formation of a visible light-responsive oxide entities of Ni2+ and Ni3+ that was further authenticated by multiple edges of variable energy in bandgap analysis. The photoluminescence (PL) spectra revealed the potential role of surface oxides in prolonging the life span of photon-induced excitons. The majority formation of Ni2O3 among the oxide entities, as the surface layer was substantiated by XRD and XPS analysis. The homogeneity, texture, and microstructure of the coated layer were examined by FESEM and HRTEM analysis. The charge retention ability as a function of the thickness of the coated layer was estimated by chronopotentiometry whereas the SPIES measurements coupled with Mott-Schottky analysis facilitated the fetching of the flat band potential as well as the semiconducting electrical nature of the coated materials. The loading of the catalysts as well as the impregnation level for optimum degradation/removal was evaluated in sunlight exposure for the removal of 4-chlorophenol (4-CP). The catalyst with optimum activity i.e. 0.5 % Ni2+ impregnated ZnO, was tested for the removal of potential carcinogens that included 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,4-dichlorophenoxyacetic acid (2,4-D). The progress of the removal process was monitored by HPLC, and the extracted data was used for kinetic studies. The efficacy of the synthesized catalysts was further evaluated for the removal of a concoction of chlorophenol isomers i.e., 2-chlorophenol (2-CP), 3-chlorophenol (3-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,5-dichlorophenol (2,5-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP), both in complete spectrum and visible region (400–800 nm) natural sunlight exposure and established the kinetics of the degradation process.