An enhanced hydrogen production by photoelectrocatalytic water splitting was obtained using extremely highly ordered nanotubular TiO2 arrays in this work. Highly ordered TiO2 nanotube arrays with a regular top porous morphology were grown by a facile and green three-step electrochemical anodization. The well ordered hexagonal concaves were uniformly distributed on titanium substrate by the first anodization, served as a template for further growth of TiO2 nanotubes. As a result, the TiO2 nanotube arrays constructed through the third anodization showed appreciably more regular architecture than that of the sample by conventional single anodization under the same conditions. The enhanced photoelectrochemical activity was demonstrated through the hydrogen generation by photoelectrocatalytic water splitting, with an exact H-2 evolution rate up to 420 mu mol h(-1) cm(-2) (10 mL h(-1) cm(-2)) in 2 M Na2CO3 + 0.5 M ethylene glycol. The photocurrent density of the third-step anodic TiO2 nanotubes is about 24 mA cm(-2) in 0.5 M KOH, which is 2.2 times higher than that of the normal TiO2 nanotubes (similar to 11 mA cm(-2)) by a single electrochemical anodization. (C) 2010 Elsevier Ltd. All rights reserved. ; National Natural Science Foundation of China [20773100, 20620130427]; National Basic Research Program of China [2007CB935603]; MOST [2007DFC40440]; National High Technology Research and Development Program of China [2009AA03Z327]