In general, ligand structure modifications can change dramatically the catalytic behavior of an organometallic complex. Modifying the electrically addressable surface with the proper choice of a metal-ligand combination to contain functional groups that induce electronic, steric, and/or electrostatic effects will allow control over the activity of the resulting catalyst. The type of support/electrode and the type of linkage between the electrode and the ligand is also essential in providing access to electrons and the electric field. Detailed discussions on different linkages affecting the electron transfer rate, reaction pathway, and catalytic performance in small molecule activation reactions will be elaborated in Section 3. The hybrid system, engendered from a logical combination of a molecular catalyst and solid support via an appropriate linkage, presents a new paradigm toward catalytic material design. Therefore, aspects to consider for a rational design of an electrocatalytic system enabled by a molecularly modified electrode include (Figure ) possible sites for modification on the ligand, the electrode material, the molecular linkage created for immobilization (covalent and non-covalent), and the solvent/electrolyte used. A careful examination of those components could lead to a logic approach for the hybrid catalytic material design and optimization.