The promising S-scheme heterojunction photocatalysts are considered as a novel frontier due to their superiority in various solar-driven energy-related applications. Recently, a novel atom-specific tailoring strategy has been introduced on the construction of S-scheme heterojunction for promoting the electronic transferability. The S-scheme heterojunction is regulated by integrating high-crystalline carbon nitride with Co-doped CeO₂. Specifically, this atom-specific regulation of S-scheme heterojunction boosts directional electron-driving effect towards functionalized Co sites, benefit-ing for effective photogenerated charge carrier transferability. Moreover, a series of tracking characterizations show that Co-embedded modification promotes CO₂ photoreduction into hydrogenation steps, resulting in high performance towards CO₂-to-CH₄ photoreduction, which provides new opportunities for the development of multifunctional cooperation in heterogeneous photocatalysis.