Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO ₂ Reduction to C _n H _2n+1 OH ( <i>n</i> =1, 2)

Efficient synthesis of C_nH_2n+1OH (n=1, 2) via photochemical CO₂ reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare earth dual single atoms (SAs) catalysts containing ErN₆ and NdN₆ moieties, fabricated via an atom-confinement and coordination method. The dual Er-Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g^-1 h^-1 and 987.7 μmol g^-1 h^-1 for CH₃CH₂OH and CH₃OH, respectively. Through a combination of theoretical calculation, XAFS analysis, aberration-corrected HAADF-STEM, and in-situ FTIR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C-C bond formation, while Nd SAs provide the necessary *CO for C-C coupling in C₂H₅OH synthesis under visible light. Furthermore, the experiment and DFT calculation elucidate that the variety of electronic states induced by 4 f orbitals of the Er SAs and the p-f orbital hybridization of Er-N moieties enable the formation of charge-transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO₂ to C_nH_2n+1OH (n=1, 2) via a novel rare earth-based dual SAs photocatalysis approach.