ZnO-incorporated mesostructured silica nanoparticles (MSN) catalysts (ZM) were prepared by the introduction of Zn ions into the framework of MSN via a simple electrochemical system in the presence of various concentrations of NH4OH aqueous solution. The physicochemical properties of the catalysts were studied by XRD, Si-29 MAS NMR, nitrogen adsorption-desorption, FE-SEM, TEM, FTIR, and photoluminescence spectroscopy. Characterization results demonstrated that the alkaline aqueous electrolyte simply generated abundant silanol groups on the surface of the catalysts as a consequence of desilication to form the hierarchical-like structure of the MSN. Subsequent restructuring of the silica network by the creation of oxygen vacancies and formation of Si-O-Zn during the electrolysis, as well as formation of new Si-O-Si bonds during calcination seemed to be the main factors that enhanced the catalytic performance of photodecolorization of methyl orange. A ZM prepared in the presence of 1.0 M NH4OH (ZM-1.0) was determined to be the most effective catalyst. The catalyst displays a higher first-order kinetics rate of 3.87 x 10(-1) h(-1) than unsupported ZnO (1.13 x 10(-1) h(-1)) that prepared under the same conditions in the absence of MSN. The experiment on effect of scavengers showed that hydroxyl radicals generated from the three main sources; reduced O-2 at the conduction band, decomposed water at the valence band and irradiated H2O2 in the solution, are key factors that influenced the reaction. It is also noted that the recycled ZM-1.0 catalyst maintained its activity up to five runs without serious catalyst deactivation. (C) 2015 Elsevier B.V. All rights reserved.