Dual‐atom‐site catalysts (DACs) have emerged as a new frontier in heterogeneous catalysis because the synergistic effect between adjacent metal atoms can promote their catalytic activity while maintaining the advantages of single‐atom‐site catalysts, such as almost 100 % atomic efficiency and excellent hydrocarbon selectivity. In this study, cobalt‐based atom site catalysts with a Co2–N coordination structure were synthesized and used for photodriven CO2 reduction. The resulting CoDAC containing 3.5 % Co atoms demonstrated a superior atom ratio for CO2 reduction catalytic performance, with 65.0 % CH4 selectivity, which far exceeds that of cobalt‐based single‐atom‐site catalysts (CoSACs). The intrinsic reason for the superior activity of CoDACs is the excellent adsorption strength of CO2 and CO* intermediates at dimeric Co active sites.