α-Fe2O3 nanorod arrays were fabricated by a low-temperature aqueous chemical growth (ACG) technique and followed by an annealing process. For the surface doping of α-Fe2O3 nanorods, β-FeOOH nanorods obtained via ACG were coated with a thin layer of Cr3+ precursor solution by spin coating, and then underwent the annealing treatment in air. Conducting polymer polypyrrole (PPy) decorated α-Fe2O3 nanorods were prepared by electrodeposition method using malic acid contained pyrrole aqueous solution. Primary results showed that the photocurrents of α-Fe2O3 nanorod array photoanodes were greatly enhanced by surface doping of Cr3+, as well as PPy decoration. This might be due to the retarded charge recombination and promoted surface reaction rate of photogenerated holes with water. Further investigation on surface modification of α-Fe2O3 nanorod array photoanodes is currently conducted in our group.