Electrochemical reduction of carbon dioxide represents an attractive possibility for valorization of this abundant carbon feedstock while simultaneously removing it from the atmosphere. Enzymes that fix carbon dioxide feature precisely positioned amino acid residues in the secondary coordination sphere in order to modulate reaction energetics. This precedent motivates the design of molecular catalysts with rationally tunable functional groups in the second coordination sphere, which allow for a better understanding of the role of the local chemical environment. Here, we present recent studies on the synthesis and electrochemical behavior of molecular CO₂ reduction catalysts and the importance of identity, positioning, and tunability of the second coordination sphere in modifying activity.