Organic-inorganic hybrid S-scheme heterojunctions have emerged as a pivotal system for overcoming the efficiency bottleneck of traditional photocatalysis. They integrate the structural designability of organic phases and high stability of inorganic phases, while retaining strong redox capability and suppressing charge recombination—thus realizing a synergistic advantage that single-component materials lack. Distinct from previous reviews, this article establishes “interface engineering” as the central thread, systematically integrating the entire research chain of organic-inorganic hybrid S-scheme heterojunctions from design and regulation to application. First, we propose a three-dimensional classification framework that goes beyond conventional material-based taxonomies, categorizing systems according to organic-phase type, interfacial interaction mode, and inorganic-component function, thereby establishing universal design principles and analyzing structure–performance relationships. Subsequently, we elaborate the interfacial charge-regulation mechanisms, such as built-in electric fields, defect engineering, and band matching, and emphasize how advanced characterization techniques (e.g., femtosecond transient absorption spectroscopy, in-situ X-ray photoelectron spectroscopy) coupled with theoretical modeling decode interface dynamics, enabling cross-scale correlation from microscopic charge transfer to macroscopic catalytic performance. Beyond summarizing applications in energy conversion (e.g., H2 production, CO2 reduction) and environmental remediation (e.g., pollutant degradation, heavy-metal reduction) together with their performance-enhancement principles, we directly address the core challenges for industrial translation, including insufficient interfacial stability, difficulties in mechanism quantification, and bottlenecks in large-scale fabrication. Finally, future directions such as dynamic interface design, multi-functional integration, and industrialization exploration are outlined. This review aims to provide comprehensive and unique guidance for designing high-performance S-scheme heterojunctions, advancing photocatalytic technology to address energy and environmental issues, and thereby building an interdisciplinary bridge toward carbon neutrality. Proposes an innovative three-dimensional classification framework: Breaking through traditional material-centric classification criteria, it establishes universal design principles for S-scheme heterojunctions by integrating organic phase diversity, modes of interfacial interaction, and functional roles of the inorganic component. Elucidates interfacial charge kinetics mechanisms: Systematically reveals the core roles of interface engineering, such as built-in electric field enhancement and defect-mediated synergy. This enables precise control over charge separation, boosting efficiency by 50–80% while retaining strong redox capabilities. Bridges fundamental research and practical application: Deeply integrates advanced characterization, theoretical modeling, and performance analysis to propose a practical "science-technology-industry" roadmap, aiming to address the core challenges in scaling up photocatalytic technology for energy and environmental applications.
Zha et al. (Mon,) studied this question.