Photoelectrochemical (PEC) water oxidation using hematite (alpha-Fe2O3) is of great interest in terms of solar fuels and artificial photosynthesis. In this study. Cd-incorporated nanocrystalline hematite films (Cd-Fe2O3) supported on conducting glass have been prepared via co-electrodeposition of aqueous Fe(III) and Cd(II) with varying Cd: Fe atomic ratios (up to 3.2 at.%) and optimized for their PEC performances under a simulated solar light (AM 1.5-irradiation). Surface analysis indicates that the Cd co-deposition increases the hematite particle size from ca. 50 nm to 70-100 nm due to interparticle agglomeration and decreases the overall UV-Vis absorbance of hematite. X-ray photoelectron spectroscopic study also indicates that Cd incorporation shifts the binding energy of oxygen atoms to lower energy direction whereas it does not affect the binding energy of Fe 3d. This suggests that Cd exists mainly as CdO and/or Cd(OH)(2) in the hematite surface. When an optimal level of Cd content (similar to 1 at.%) is electrodeposited, the photocurrent of hematite film is significantly enhanced by a factor of ca. four at E = 1.23 V-RHE under AM 1.5-irradiation and the photoactive spectral region is red-shifted. Electrochemical impedance spectroscopic analysis further reveals that the flat band potential of hematite is shifted by ca. -30 mV to negative potential direction and the charge transfer resistance (R-ct) is significantly reduced by Cd incorporation. Detailed surface analyses, optimization for preparation condition of hematite films, and discussion for PEC behaviors were described. (C) 2011 Elsevier B.V. All rights reserved.