Hexagonal ZnIn2S4 photocatalysts with 3D-hierarchical persimmon-like shape have been successfully synthesized via an oleylamine (OA)-assisted solvothermal method. Hydrogen evolution experiments revealed that the obtained hierarchical ZnIn2S4 possessed good photocatalytic activity, e.g. hydrogen production rate reached to 220.45 mu mol h(-1) and the quantum yield was up to 13.16% when 3% Pt was loaded. Further delicate tuning the percentage of exposed facet of the obtained ZnIn2S4 crystals, it was found that the increase of {006} facets, terminated by metal ions, would improve their photocatalytic activity, and the relationship between the crystal structure and photocatalytic properties had been studied. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.