TiO(2) nanotube arrays (TNTAs) sensitized by palladium quantum dots (Pd QDs) exhibit highly efficient photoelectrocatalytic hydrogen generation. Vertically oriented TNTAs were prepared by a three-step electrochemical anodization. Subsequently, Pd QDs with uniform size and narrow size distribution were formed on TiO(2) nanotubes by a modified hydrothermal reaction (i.e., yielding nanocomposites of Pd QDs deposited on TNTAs, Pd@TNTAs). By exploiting Pd@TNTA nanocomposites as both photoanode and cathode, a substantially increased photon-to-current conversion efficiency of nearly 100% at λ = 330 nm and a greatly promoted photocatalytic hydrogen production rate of 592 μmol·h(-1)·cm(-2) under 320 mW·cm(-2) irradiation were achieved. The synergy between nanotubular structures of TiO(2) and uniformly dispersed Pd QDs on TiO(2) facilitated the charge transfer of photoinduced electrons from TiO(2) nanotubes to Pd QDs and the high activity of Pd QDs catalytic center, thereby leading to high-efficiency photoelectrocatalytic hydrogen generation.