Herein, we report the surface treatment on Zr4+/Al3+ codoped alpha-Fe2O3 photoanode for high-performance photoelectrochemical water splitting. A high-temperature quenching exhibits the Zr4+/Al3+ codoping in alpha-Fe2O3 photoanode without damaging morphology. The presence of Zr4+/Al3+ codoping shows a cathodic shift in onset potential, but lack of increment in photocurrent reveals the major role of passivation and the minimum doping effect of aluminum. Additionally, CoOx cocatalyst exhibits increment in photocurrent with the greater cathodic shift in onset potential than the pristine alpha-Fe2O3 nanorods. The CoOx surface-reworked Zr4+/Al3+ codoped alpha-Fe2O3 photoanode displays the highest photocurrent of 1.5 mA/cm(2) at 1.23 V vs. RHE (76% increment over the pristine alpha-Fe2O3) and 0.7 mA/cm(2) at 1.0 V vs. RHE (102% increment over the pristine alpha-Fe2O3). The systematic characterization carried out using x-ray diffraction and scanning electron microscopy confirms that after Zr4+/Al3+ codoping, and surface treatment, the crystalline structure, and morphology of the photoanodes remains unchanged. X-ray photoelectron spectroscopy confirmed the existence of Zr4+/Al3+ codopants in the hematite nanostructure. The electrochemical properties of the photoanode suggest that Al3+ and Zr4+ codoping, as well as surface treatment with CoOx, cocatalyst lowers charge transfer resistance across the FTO/hematite interface, and hematite/electrolyte interface. This designs not only lowers onset potential but also offers the blueprint for the development of an efficient catalyst for solar water oxidation. (C) 2019 Elsevier Ltd. All rights reserved.