Various morphologies of CdS photocatalysts, including nanoparticles, nanorods, urchin-like shape and nanowires were prepared via a solvothermal process by tailoring the solvent. Based on both experimental and theoretical simulation investigation, the microstructure evolution mechanism was specified. Visible-light-driven photocatalytic activities for hydrogen production over the different CdS products were compared and rationalized. CdS nanowires prepared with the utilization of tetraethylenepentamine (TEPA) as solvent and L-cysteine as sulfur precursor displayed excellent photocatalytic Ha-production activity of 803 mu mol h(-1) with quantum efficiency (QE) of 37.7% at 420 nm. The enhanced photocatalytic activity was ascribed to the high purity, good crystallinity, and unique microstructure and band structure, which was favorable for transfer of photogenerated carriers and thus reduced the recombination of electron-hole pairs. This work showed that the nature of solvent had significant influence on the photocatalytic Ha-production activity of CdS, which adds knowledge on designing photocatalysts for visible-light-driven photocatalytic hydrogen evolution. (C) 2014 Elsevier B.V. All rights reserved.