We demonstrate the effect of hydrogen plasma treatment on hematite films as a simple and effective strategy for modifying the existing substrate to improve significantly the band edge positions and photoelectrochemical (PEC) performance. Plasma treated hematite films were consist of mixed phases (Fe sub(3)O sub(4): alpha -Fe sub(2)O sub(3)) which was confirmed by XPS and Raman analysis, treated films also showed higher absorption cross-section and were found to be a promising photoelectrode material. The treated samples showed enhance photocurrent densities with maximum of 3.5 mA/cm super(2) at 1.8 V/RHE and the photocurrent onset potentials were shifted from 1.68 V sub(RHE) (untreated) to 1.28 V sub(RHE) (treated). Hydrogen plasma treatment under non-equilibrium conditions induced a valence dynamics among Fe centers in the sub-surface region that was sustained by the incorporation of hydrogen in the hematite lattice as supported by the density functional theory calculations.