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In summary, the ultrathin multimetallic phosphochalcogenides photocatalysts exhibit excellent photocatalytic activity. Among them, the ultrathin structure can provide more active sites, which is conducive to CO2 adsorption and activation, while the Cu–In dual sites act as tandem catalytic sites to accelerate C=O bond activation and C–C bond coupling. Despite this research has significant scientific value and theoretical significance for achieving carbon emission reduction and resource utilization of CO2 as well as guiding the design and preparation of highly efficient multimetallic 2D layered catalysts, the bottlenecks of large-scale preparation and the considerations on cost, stability and longevity of these 2D catalysts for industrial applications still remain a significant challenge. Furthermore, improving product selectivity and integrating such catalytic processes into existing industrial systems will contribute significantly to sustainable industrialization.