Hematite (i.e., α-Fe2O3) nanorod photoanodes passivated with a phosphorus overlayer have been fabricated by decomposing sodium hypophosphite (NaH2PO2) at a low temperature over the hematite nanorod surface. Extensive scanning electron microscopy, transmission electron microscopy, x-ray diffractometry and UV-vis spectroscopy characterizations confirm that conformal deposition of an amorphous phosphorus overlayer does not change the crystal structure, morphology, and optical absorption properties of hematite photoanodes. X-ray photoelectron spectroscopy reveals that phosphorus in the deposited overlayer exists in an oxidized state. Comprehensive steady-state polarization, transient photocurrent response, and impedance spectroscopy measurements as well as Mott-Schottky analysis manifest that the phosphorus overlayer is able to effectively passivate surface states and suppress electron-hole recombination, substantially enhancing the photocurrent for water oxidation. Combining the phosphorization treatment with two-step thermal activation, a photocurrent density of 1.1 mA cm(-2) is achieved at 1.23 V versus reversible hydrogen electrode under illumination of 100 mW cm(-2), ca 55 times higher than that of the non-activated pristine hematite photoanode measured under the same conditions. The simple and fast phosphorization strategy we present here can be readily applied to passivate surfaces of other semiconductor photoelectrodes to improve their photoelectrochemical performance.