The conversion and storage of solar energy to chemical energy via artificial photosynthesis holds significant potential for optimizing the energy situation and mitigating the global warming effect. Photocatalytic water splitting utilizing particulate semiconductors offers great potential for the production of renewable hydrogen, while this cross-road among biology, chemistry, and physics features a topic with fascinating interdisciplinary challenges. Progress in photocatalytic water splitting has been achieved in recent years, ranging from fundamental scientific research to pioneering scalable practical applications. In this review, we focus mainly on the recent advancements in terms of the development of new light-absorption materials, insights and strategies for photogenerated charge separation, and studies towards surface catalytic reactions and mechanisms. In particular, we emphasize several efficient charge separation strategies such as surface-phase junction, spatial charge separation between facets, and polarity-induced charge separation, and also discuss their unique properties including ferroelectric and photo-Dember effects on spatial charge separation. By integrating time- and space-resolved characterization techniques, critical issues in photocatalytic water splitting including photoinduced charge generation, separation and transfer, and catalytic reactions are analyzed and reviewed. In addition, photocatalysts with state-of-art efficiencies in the laboratory stage and pioneering scalable solar water splitting systems for hydrogen production using particulate photocatalysts are presented. Finally, some perspectives and outlooks on the future development of photocatalytic water splitting using particulate photocatalysts are proposed.