Electrochemical and photoelectrochemical catalysis of surface-passivated zinc oxide (ZnO) nano structures with three different metal oxides were investigated. Initially, vertically aligned ZnO nanorods structures were developed over conductive substrates by a two-step approach and then passivated with an ultrathin zinc hydroxide, that is, Zn(OH)(2), cobalt oxide, that is, CoO, and Zn(OH)(2)/CoO as bilayer, by electrochemical deposition. Compared with the pristine ZnO structures, the surface-passivated nano structures possess slightly rough surfaces, whereas their crystal structure remains unchanged. From electrochemical catalysis studies under dark and illumination, it is noticed that vertically aligned ZnO nanostructures passivated with narrow band-gap CoO layers have a predominant water oxidation performance than that of the structures passivated with other oxide materials. It is mainly attributed to the eradication of surface states present on ZnO nanorods. Interestingly, the structures passivated with bilayers, that is, Zn(OH)(2)/CoO, showed significant stability and durability (similar to 103% retention in current density@60th min) with a continuous oxygen evolution reaction process for long durations. (C) 2021 Elsevier Ltd. All rights reserved.