Gold nanoparticles have been deposited on the surface of hematite nanorod array photoanode to improve the photoelectrochemical water splitting performance. The Au nanoparticles induce the Fermi level equilibration, the surface catalysis, and the plasmonic enhancement effects in the Au/hematite photoanode. The Fermi level equilibration effect promotes the extraction of photo-generated charge carriers, suppressing the charge recombination. Surface catalysis effect reduces the overpotential for photoelectrochemical water oxidation. In the Au/hematite sample, the Fermi level equilibration and the surface catalysis effect make major contribution to photocurrent enhancement while the plasmonic effect makes a little contribution. In addition, the Au@SiO2 particle has been immobilized on hematite nanorod array surface that has been passivated. In the Au@SiO2/hematite sample, the photocurrent enhancement originating from plasmonic effects is negligible. Both the Femi level equilibration and the surface catalysis effects were excluded due to the isolated Au and hematite while surface passivation is mainly responsible for the photocurrent enhancement.