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.