Photocatalytic overall water splitting (OWS) using suspended particulate photocatalysts to produce green hydrogen has inspired continuous interest due to its low cost for easy large-scale application. The two-step photoexcitation system (Z-scheme) mimicking natural photosynthesis was proposed to efficiently use visible light for realization of efficient conversion of solar irradiation. In this Perspective, we will introduce recent advances in redox-based Z-scheme OWS systems, including iodine-based, iron-based, metal complex-based, and other special ion redox couples. The advantages and challenges of each couple and the factors affecting the Z-scheme OWS efficiency are discussed in detail. Finally, the challenges and feasible solutions for the achievement of highly efficient Z-scheme OWS are then outlined. This Perspective provides guidance on how to construct a Z-scheme OWS system and enhance photocatalytic performance.