Atomically dispersed metal atoms (ADMAs) on carbon supports emerged as catalysts which can bridge the merits of both homogeneous and heterogeneous systems and display high selectivity towards electrochemical conversion of carbon dioxide (CO2) to carbon monoxide (CO). Various local coordination structures have been suggested in the ADMAs to achieve high selectivity. In this chapter, the structure–function relationship of ADMAs is correlated with the structure–function strategy used by natural enzymes to advance our understanding further and to elucidate the structural implication on the CO2 reduction activity. In addition, expanding the applicability of the ADMAs to attain C2 to multi carbon products, the strategies already used in homogeneous systems and theoretical studies are highlighted. The methods to be adopted in terms of synthesizing diatom or multi-atom catalysts and introducing the factors which tune the cooperative effects to obtain hydrocarbon products are suggested and discussed in detail.