Solar driven semiconductor photocatalytic water splitting to produce hydrogen is an extremely charming process by storing photon energy in chemical bonds. In the present study, composite semiconductor TiO2/CdS was structured into uniform and porous double-shelled hollow sphere with cocatalyst platinum selectively loaded onto the internal wall. The SEM, TEM, STEM, XRD, BET and EDS elemental distribution etc. were employed to evidence the formation of the targeted photocatalyst. It was demonstrated that the material has a high efficiency of visible-light-driven hydrogen evolution (296 mu mol.h(-1)/10 mg) with an apparent quantum efficiency (QE) of 14.5% at wavelength of 420 nm. Comparative experiment analysis and time-resolved infrared absorption study suggested that the high photocatalytic activity of the catalyst is attributed to the vectorial electron transfer (CdS -> TiO2 -> Pt) and the spatial separation of reduction and oxidation active surfaces achieved by the special morphology. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.