Semiconductor photocatalysts have attracted increased attention due to their great potential for solving energy and environmental problems. The formation of Z‐scheme photocatalytic systems that mimic natural photosynthesis is a promising strategy to improve photocatalytic activity that is superior to single component photocatalysts. The connection between photosystem I (PS I) and photosystem II (PS II) are crucial for constructing efficient Z‐scheme photocatalytic systems using two photocatalysts (PS I and PS II). The present review concisely summarizes and highlights recent state‐of‐the‐art accomplishments of Z‐scheme photocatalytic systems with diverse connection modes, including i) with shuttle redox mediators, ii) without electron mediators, and iii) with solid‐state electron mediators, which effectively increase visible‐light absorption, promote the separation and transportation of photoinduced charge carriers, and thus enhance the photocatalytic efficiency. The challenges and prospects for future development of Z‐scheme photocatalytic systems are also presented.

Hydrogen is a very promising candidate as a future energy carrier. It is attractive to produce hydrogen from solar energy and seawater, the most abundant renewable energy source and the most abundant natural resource on the earth. To date, there is no report on a stable photoelectrode with a high incident photon conversion efficiency (IPCE) in seawater splitting under irradiation by visible light. Herein, we report an efficient and stable system for seawater splitting based on a multi-metal oxide BiVO₄ after modification. The results indicated that modified BiVO₄ had a photocurrent density of 2.16 mA cm⁻² at 1.0 V_RHE in natural seawater under AM 1.5G sunlight (1000 W m⁻²) and exhibited the highest IPCE at 1.0 V_RHE in the visible light region of 440–480 nm among all known oxide photoanodes.