The Si and Ti codoped hematite (α-Fe2O3) photoanode film was dripped by Na3RhCl6·12H2O alkaline solution to negatively shift the onset potential of α-Fe2O3 photoanode by ∼ 200 mV. The photocurrent densities of as-treated and untreated α-Fe2O3 are 0.6, and 0.08 mA/cm2, respectively at 0 V vs. Ag/AgCl in the electrolyte of 1 M NaOH aqueous solution under 500 W xenon illumination. The IPCE (incident photon to current efficiency) of the as-treated α-Fe2O3 is 5.2% at 365 nm, 0 V vs. Ag/AgCl. A plausible explanation is proposed for the enhanced α-Fe2O3 photoelectrochemical responses. The result shows that rhodium could be ranked as an efficient oxygen evolution catalyst.