Hierarchical Mn2O3 microspheres have been prepared Via polyol-mediated solvothermal method. The as prepared hierarchical microspheres is about 8-10 mu m in diameter assembled with porous nanosheets which favors charge transport. The formation process has been studied which is to form nanosheet first and then to self-assemble and finally to grow spheres. The band structure of Mn2O3 microspheres is confirmed through XPS valence spectrum and UV-vis,verfiying that it is suitable for hydrogen reduction. The H-2 production efficiency of hierarchical Mn2O3 microspheres is found to three time higher than that of Mn2O3 particles. The promoted photocatalytic hydrogen production efficiency could be attributed to the interesting hierarchical structure, large surface area and suitable band gap. (C) 2016 Elsevier Ltd. All rights reserved.