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As the world decides on the next giant step for the renewable energy revolution, scientists have begun to reinforce their headlong dives into the exploitation of solar energy. Hitherto, numerous attempts are made to imitate the natural photosynthesis of plants by converting solar energy into chemical fuels which resembles the “Z‐scheme” process. A recreation of this system is witnessed in artificial Z‐scheme photocatalytic water splitting to generate hydrogen (H2). This work outlines the recent significant implication of the Z‐scheme system in photocatalytic water splitting, particularly in the role of electron mediator and the key factors that improve the photocatalytic performance. The Review begins with the fundamental rationales in Z‐scheme water splitting, followed by a survey on the development roadmap of three different generations of Z‐scheme system: 1) PS‐A/D‐PS (first generation), 2) PS‐C‐PS (second generation), and 3) PS‐PS (third generation). Focus is also placed on the scaling up of the “leaf‐to‐tree” challenge of Z‐scheme water splitting system, which is also known as Z‐scheme photocatalyst sheet. A detailed investigation of the Z‐scheme system for achieving H2 evolution from past to present accompanied with in‐depth discussion on the key challenges in the area of Z‐scheme photocatalytic water splitting are provided., The significant implication of Z‐scheme systems of different generations in photocatalytic water splitting, from past to present, is outlined and reviewed. The rationales and mechanisms in Z‐scheme systems, followed by a survey on the development roadmap of Z‐scheme systems from the first to third generation are presented. Lastly, the rapid emergence of particulate Z‐scheme photocatalyst sheets is outlined.