A unique nanostructured rod-like morphol. of hematite (α-Fe2O3), designed with no grain boundaries, has been investigated for the aim of a direct splitting of water at the hematite/electrolyte interface. Photoelectrochem. properties were studied by steady-state measurements on electrodes with controlled morphol. and film thickness in aq. electrolyte. The hematite electrodes were able to generate incident photon-to-current efficiencies (IPCEs) of ∼8% by illumination through the substrate with a wavelength of 350 nm and a light intensity of 0.1 mW cm-2 without any applied voltage. On the basis of light intensity studies, it is concluded that charge carrier recombinations due to the poor semiconductor properties in combination with slow oxidn. kinetics at the hematite nanorods/electrolyte interface are the dominating problems. However, the high IPCE values obtained indicates that purpose-built nanorods of hematite is one significant way to strikingly lower the recombination rate of hematite material.