In this study highly-ordered titania nanotube arrays of variable wall-thickness and length are used to photocleave water under ultraviolet irradiation. We demonstrate that the wall thickness, and length, of the nanotubes can be controlled via anodization bath composition and temperature. The nanotube length and wall thickness are key parameters influencing the magnitude of the photoanodic response and the overall efficiency of the water-splitting reaction. For 22 nm inner-pore diameter nanotube-arrays 6 μm in length, with 9 nm wall thickness, upon 320–400 nm illumination at an intensity of 100 mW/cm2, hydrogen gas was generated at the power-time normalized rate of 51 mL/hr•W at an overall conversion efficiency of 12.5%. To the best of our knowledge, this hydrogen generation rate is the highest reported for a titania-based photoelectrochemical cell.