TiO2 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 TiO2 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 lambda = 330 nm and a greatly promoted photocatalytic hydrogen production rate of 592 mu mol.h(-1).cm(-2) under 320 mW.cm(-2) irradiation were achieved. The synergy between nanotubular structures of TiO2 and uniformly dispersed Pd QDs on TiO2 facilitated the charge transfer of photoinduced electrons from TiO2 nanotubes to Pd QDs and the high activity of Pd QDs catalytic center, thereby leading to high-efficiency photoelectrocatalytic hydrogen generation. ; National Natural Science Foundation of China [51072170, 21021002]; National Basic Research Program of China [2012CB932900]; Academic New Artist Ministry of Education Doctoral Post Graduate of China; Georgia Institute of Technology