Here we report on Bi2O3 clusters immobilized on anatase TiO2 nanostructures for an enhanced rate of photocatalytic H-2 evolution. Structural, morphological, and optical properties of the Bi2O3@TiO2 nanocomposite (BT) were characterized by a series of techniques including X-ray diffraction, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy and electrochemical impedance spectroscopy. The catalytic H-2 evolution experiments were carried out under different light sources: natural solar light, LED UV (365 +/- 5 nm) and LED visible (420 +/- 5 nm) light source. Under the solar light a pristine anatase TiO2 nanostructured (TNS) catalyst generated 4.20 mmol h(-1) g(-1), whereas in the presence of Bi2O3@TNS showed much higher H-2 production 26.02 mmol h(-1) g(-1). The photocatalytic activity of the BT and its reproducible performance for five recycles is ascribed to an efficient separation of photogenerated charge carriers. A plausible reaction mechanism for the H-2 generation is proposed. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.