The so‐called Z‐scheme is a means of utilizing photo‐induced electrons from a photosystem and has consistently motivated the design of synthetic photocatalytic systems. Although progress has been made in many pioneering studies on an inorganic‐based Z‐scheme, there have been no reports of a hybrid Z‐scheme for an inorganic and a photosystem. Here, a hybrid Z‐scheme is demonstrated by integrating a platinized photosystem I (PSI) and BiVO₄ for hydrogen production. Up to now, PSI‐driven systems have been limited to a one‐step photoreduction reaction using sacrificial reductants. In this hybrid Z‐scheme, step‐wise charge separation in PSI and BiVO₄ enables the production of hydrogen from only water under visible light. PSI and BiVO₄ are conjugated via metal mediators to form an all‐linked structure. The novel design exhibits potential for the development of a protein hybrid system for electrochemical devices, sensors, and a solar energy conversion system.