Anodized tubular titania (TiO2) electrodes (ATTEs) are prepared and used as both the photoanode and the cathode substrate in a photoelectrochemical system designed to split water into hydrogen with the assistance of an enzyme and an external bias of 1.5V. In particular, the ATTE used as the cathode substrate for the immobilization of the enzyme is prepared by two methods-adsorption and crosslinking. Results show that the optimized amount of enzyme is 10.98 units for the slurried enzyme, 3.66 units for the adsorbed one and 7.32 units for the crosslinked one, and the corresponding hydrogen evolution rates are 33.04, 148.58 and 234.88 mu mol h(-1), respectively. The immobilized enzyme, specifically the chemically crosslinked one, seems to be much superior to the slurried enzyme, due to the enhanced charge-transfer process that is caused by the lower electrical resistance between the enzyme and the ATTE. This results in a greater number of accepted electrons and a larger amount of enzymes able to deal with the electrons. (c) 2008 Elsevier B.V. All rights reserved.