It is well-established that electrocatalysts with biologically inspired moieties provide advantageous qualities for the efficient transformation of fossil fuel combustion products, such as carbon dioxide, into value-added products. Herein, we present a family of Re(bpy)(CO)3Cl electrocatalysts with pendant NH2 groups in the 4,4′-, 5,5′-, and 6,6′-positions of the bipyridine backbone with the objective of determining the effects of combined primary- and secondary-sphere interactions on the reduction of CO2 to CO. Cyclic voltammetry studies under CO2 indicate that the catalytic onset potential is more positive for 6,6′-NH2-Re, indicating that proximity of the available pendant protons to the metal center is beneficial during catalysis. Controlled potential electrolysis studies demonstrate that, similar to 6,6′-NH2-Re, 4,4′-NH2-Re displays a dependence of Faradaic efficiency (FE) on catalytic potential, reaching a maximum FECO of 91% at −2.40 V. This FE is greater than that observed for 6,6′-NH2-Re but occurs at a more negative potential. Density functional theory (DFT) calculations were performed to compare the HOMO-LUMO gap of these complexes, and the following trend of 4,4′-NH2-Re > 6,6′-NH2-Re > 5,5′-NH2-Re was determined. Mulliken electron population analysis indicates a greater degree of electron density on the metal center for 6,6′-NH2-Re compared to its related congeners, in agreement with the electrolysis studies which illustrate a more favorable CO2 reduction for 6,6′-NH2-Re. Ultimately, it is important that the various catalytic parameters are properly balanced to provide the greatest overall catalytic activity.