Integrating natural and artificial photosynthetic platforms is an important approach to developing solar-driven hybrid systems with exceptional function over the individual components. A natural–artificial photosynthetic hybrid platform is formed by wiring photosystem II (PSII) and a platinum-decorated silicon photoelectrochemical (PEC) cell in a tandem manner based on a photocatalytic-PEC Z-scheme design. Although the individual components cannot achieve overall water splitting, the hybrid platform demonstrated the capability of unassisted solar-driven overall water splitting. Moreover, H₂ and O₂ evolution can be separated in this system, which is ascribed to the functionality afforded by the unconventional Z-scheme design. Furthermore, the tandem configuration and the spatial separation between PSII and artificial components provide more opportunities to develop efficient natural–artificial hybrid photosynthesis systems.