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Solar‐driven photocatalytic CO₂ reduction is regarded as a promising way to simultaneously mitigate the energy crisis and CO₂ pollution. However, achieving high efficiency of photocatalytic CO₂ reduction, especially without the assistance of sacrifice reagents or extra alkaline additives, remains a critical issue. Herein, a photocatalyst of 3D ordered macroporous N‐doped carbon (NC) supported CdS quantum dots (3DOM CdSQD/NC) is successfully fabricated toward photocatalytic CO₂ reduction via an in situ transformation strategy. Additionally, an amines oxidation reaction is introduced to replace the H₂O oxidation process to further boost the photocatalytic CO₂ reduction efficiency. Impressively, 3DOM CdSQD/NC exhibits superior activity and selectivity in photocatalytic CO₂ reduction coupled with amines oxidation, affording a CO production rate as high as 5210 µmol g⁻¹ h⁻¹ in the absence of any sacrificial …