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Despite suffering from slow charge‐carrier mobility, photocatalysis is still an attractive and promising technology toward producing green fuels from solar energy. An effective approach is to design and fabricate advanced architectural materials as photocatalysts to enhance the performance of semiconductor‐based photocatalytic systems. Herein, metal–organic‐framework‐derived hierarchically ordered porous nitrogen and carbon co‐doped ZnO (N‐C‐ZnO) structures are developed as nanoreactors with decorated CoO_x nanoclusters for CO₂‐to‐CO conversion driven by visible light. Introduction of hierarchical nanoarchitectures with highly ordered interconnected meso–macroporous channels shows beneficial properties for photocatalytic reduction reactions, including enhanced mobility of charge carriers throughout the highly accessible framework, maximized exposure of active sites, and inhibited recombination …