In this study highly ordered titania nanotube arrays of variable wall thickness 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 temperature. We find that the nanotube wall thickness is a key parameter influencing the magnitude of the photoanodic response and the overall efficiency of the water-splitting reaction. For 22 nm inner pore diameter nanotube arrays, those fabricated in a 5 degrees C anodization bath, 224 nm length and 34 nm wall thickness produced a photoanodic response that was thrice that of a nanotube array fabricated in a 50 degrees C anodization bath, 120 nm length and 9 nm wall-thickness. At high anodic polarization, above 1 V, the quantum efficiency under 337 nm illumination was greater than 90%. For the 5 degrees C anodization bath samples (22 nm pore-diameter, 34 nm wall thickness), upon 320-400 nm illumination at an intensity of 100 mW/cm(2), hydrogen gas was generated at the power-time normalized rate of 960 micromol/h W (24 mL/h W) at an overall conversion efficiency of 6.8%. To the best of our knowledge, this hydrogen generation rate is the highest reported for a titania-based photoelectrochemical cell.