Throughout this review, we tried to convey the potential advantages of employing a molecularly modified electrode/electrically addressable material as a catalyst for electrocatalytic reactions related to energy conversion and transformations strongly impacted by an electric field. We started by demonstrating common methods for the surface immobilization of molecules, mainly non-covalent and covalent interactions. We included several commonly employed electrically addressable materials, such as carbonbased, metal, and oxide-based electrodes. Common strategies being applied to modify each type of electrode material were discussed, along with techniques for characterizing the resulting material. To provide a handle for immobilization, certain modifications are required to be implemented on the molecular component. The resulting "linkage" to the surface often plays an important role in manipulating electron transfer and determining the reaction mechanism. With an overview of some recent publications working on redox and non-redox reactions utilizing molecularly modified electrodes as a catalyst, we discussed the importance of the molecular component of the hybrid system that provides handles to optimize the reactivity and selectivity of the reaction studied by modifying the molecular structure. Such modifications on the molecular level could result in inductive electronic effects, steric effects, as well as electrostatic effects. We hope to encourage further designs and investigations on combining the advantages of homogenous molecular catalysts and heterogeneous electrode materials for optimal activity, selectivity, durability, and efficiency of a catalytic system. To provide an excellent reference point for beginners in the field, we summarize the following learning points from this review and wish to inspire more people to explore this area.