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

Abstract Efficient synthesis of C n H 2n+1 OH ( n =1, 2) via photochemical CO 2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare earth dual single atoms (SAs) catalysts containing ErN 6 and NdN 6 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 CH 3 CH 2 OH and CH 3 OH, 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 C 2 H 5 OH 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 CO 2 to C n H 2n+1 OH ( n =1, 2) via a novel rare earth‐based dual SAs photocatalysis approach.