Contemporary electrocatalysts for the reduction of CO2 often suffer from low stability, activity, and selectivity, or a combination thereof. Mn-carbonyl complexes represent a promising class of molecular electrocatalysts for the reduction of CO2 to CO as they are able to promote this reaction at relatively mild overpotentials, whereby rare-earth metals are not required. The electronic and geometric structure of the reaction center of these molecular electrocatalysts is precisely known and can be tuned via ligand modifications. However, ligand characteristics that are required to achieve high catalytic turnover at minimal overpotential remain unclear. We consider 55 Mn-carbonyl complexes, which have previously been synthesized and characterized experimentally. Four intermediates were identified that are common across all catalytic mechanisms proposed for Mn-carbonyl complexes, and their structures were used to calculate descriptors for each of the 55 Mn-carbonyl complexes. These electronic-structure-based descriptors encompass the binding energies, the highest occupied and lowest unoccupied molecular orbitals, and partial charges. Trends in turnover frequency and overpotential with these descriptors were analyzed to afford meaningful physical insights into what ligand characteristics lead to good catalytic performance, and how this is affected by the reaction conditions. These insights can be expected to significantly contribute to the rational design of more active Mn-carbonyl electrocatalysts.