The synthesis, structural characterization, and reactivity of two iron(III) compounds with 6,6'-([2,2'-bipyridine]-6,6'-diyl)bis(4-(methyl)-2-methoxyphenol) ( me crebpy[H]2, Fe( me crebpy)Cl, 2) and 6,6'-([2,2'-bipyridine]-6,6'-diyl)bis(4-(tert-butyl)benzene-1,2-diol) ( tbu catbpy[H]4, Fe( tbu catbpy), 3) as ligands under electrochemically reducing conditions is reported. Differences in selectivity and activity for the electrocatalytic reduction of carbon dioxide (CO2) to formate (HCO2 -) were assessed via cyclic voltammetry (CV) and controlled potential electrolysis (CPE) experiments in N,N-dimethylformamide (N,N-DMF). Mechanistic studies suggest that the O atoms in the secondary coordination sphere are important for relaying exogeneous protons to the active site, enhancing the multi-site electron proton transfer (MS-EPT) activation of the catalysts, which leads to a 4-fold TOFmax increase for 2 and 2-fold for 3 in comparison to our previous studies. Depending on the strength of the interaction between the pendent moiety and the sacrificial proton donor, improvements in catalytic activity and efficiency were observed, suggesting a corresponding electronic effect from the interaction of the pendent functional groups with the Fe-bound O atom when protonated. CPE experiments indicate increasedFaradaic efficiencies (FE) for formate (85±2%) with 2, whereas 3 had a lower FE for formate of 70±8%. These results suggest that using secondary sphere moieties to modulate metal-ligand interactions and MS-EPT reactivity in the primary coordination sphere is a powerful strategy for modulating electrocatalytic activity and selectivity.