In addition to externally applied electric fields, local electric fields introduced by charged functional groups could also be employed to tune catalytic activity, for example, in organometallic catalysts. In molecular catalysis involving organometallic complexes, the supporting ligand plays a crucial role in controlling the reactivity and selectivity of the catalytically active species by tuning its electronic and steric properties. Recent studies on the effects of ligand substituents on molecular electrocatalysis emphasize the importance of considering possible through-space effects caused by the installed substituents in addition to the inductive effects (through-structure) that are commonly interpreted on the molecular level. In other words, the implementation of charged substituents on the molecular functionality being immobilized, for example, not only alters the electronic properties of that molecular functionality by donating or withdrawing electrons but also may induce electrostatic effects which may play an irreplaceable role in stabilizing key intermediates in small molecule transformations.