Morphology regulation and surface modification are crucial strategies to improving the photoelectrochemical water oxidation performance of Fe 2 O 3 photoanodes. In this study, Pluronic F127-assisted synthesis and post-treatment were adopted to achieve surface modification of FeOOH nanorods prepared by hydrothermal technique, thereby adjusting the morphology and surface properties of Fe 2 O 3 photoanodes after calcination. Although the morphology of FeOOH barely changed, the creation of porous nanorods through F127-assisted synthesis and morphological change from worm-like nanorods into nanoplates by F127-assisted post-treatment were realized, and the electrochemically active surface area, crystallinity, number of surface disorders, and photoabsorption property were affected. Furthermore, relatively high intensity of lattice defects and low-valent ferrous ions (Fe2+) were generated after F127-assisted synthesis, and charge transfer from the surface states was increased. Consequently, Fe 2 O 3 photoanode subjected to F127-assisted synthesis exhibited a reduction in the onset potential by 60 mV. The photocurrent density of Fe 2 O 3 increased by 77% at 1.23 V versus reversible hydrogen electrode following a synergistic effect of F127-assisted synthesis and post-treatment. [Display omitted] • Both F127-assisted synthesis and post-treatment can affect the morphology and surface properties of hematite. • Hematite appears as porous nanorod with existence of surface Fe2+ after F127-assisted synthesis. • Hematite appears as nanoplates after F127-assisted post-treatment. • Reduction in onset potential and increase in photocurrent density are achieved with F127-assisted modifications. • F127-assisted post-treatment introduces additional surface states on hematite. [ABSTRACT FROM AUTHOR]