We have developed thin zinc oxide (ZnO) layers protected highly conductive p-type silicon (Si) electrodes and investigated their diode and photoanode characteristics. ZnO layers have been deposited on the glass as well as p-Si substrates at a temperature of 400 degrees C by pulsed spray pyrolysis method. The crystal structure, surface morphology, and phase purity of the layers along with electrical characteristics of the heterostructures were investigated. Finally, the photocatalytic water oxidation performance of the ZnO/Si structures was studied in an alkaline electrolyte solution (pH = 10). The as-grown devices exhibited excellent diode characteristics with a turn-on voltage of 4.5 V, and applied bias-voltage dependent carrier transport mechanisms. As compared to bare Si, ZnO coated Si-based PEC devices showed good stability and durability along with very low onset potential of 0.07 V versus Ag/AgCl. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.