Hydrogen is the most efficient and the cleanest fuel. Inspired by photosynthesis, which is able to catalyze water-splitting reaction to achieve energy storage on the large scale at room temperature and neutral pH in nature, artificial systems and technology have been increasing advanced and great progresses have been made over the past decades. The three-dimensional structure of photosystem II with oxygen-evolving activity has been determined at an atomic level, which provides a thorough image with the specific position of each atom in the Mn4CaO5 cluster. These advancements have significantly enhanced our understanding of the mechanisms of water splitting in photosynthesis and offered a unique opportunity for hydrogen fuel production. In this review, the recent efforts in the area of manganese/semiconductor system for hydrogen generation were summarized with examples and discussed to highlight the operation mechanisms of this kind of catalytic configuration. A robust PS II mimic containing manganese/semiconductor nanostructure to accomplish the photo water splitting chemistry was evaluated. The development, mechanism, and future improvement of the manganese/semiconductor system were presented. The manganese/semiconductor system is highly likely to offer novel technology for hydrogen energy production. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.