In this study, a potentially universal new strategy is reported for the large-scale, low-cost fabrication of visible-light-active highly ordered heteronanostructures based on the spontaneous photoelectric-field-enhancement effect inherent in pyramidal morphology. The hierarchical vertically oriented arrayed structures comprise an active molecular co-catalyst at the apex of a visible-light-active large band gap semiconductor for low-cost solar water splitting in a neutral aqueous medium without the use of a sacrificial agent.