The applications of electrochemistry in chemical synthesis, although not discussed in detail in this review, have been established in homogenous catalysis. Furthermore, the coupling of multiple catalysts after a well-established electrochemical transformation, such as CO2 reduction, allows subsequent reactions to produce valuable products such as ethylene. Applying a compatible catalyst that allows orthogonal chemistry to occur has excellent potential in synthesizing complicated chemicals from simple building blocks. One of the challenges remains in the design of a practical, large-scale electrochemical setups. Although electrochemical cells offer proof-of-concept for some reactions, they may not be suitable for industrial applications. Notably, an electrochemical cell can switch catalysis on and off rapidly; scaling up may encounter the limitation of mass transport within the cell. A designed flow cell has been developed and adopted to address the potential issue in large-scale electrochemical synthesis. Other than the scale-up issue, another potential disadvantage of the switchable electrochemical synthesis is a low-value charge balance reaction from sacrificial counter electrodes, i.e., lithium, 139 magnesium. A way to solve the issue is to employ an integrated catalysis strategy. For example, a value-added process (i.e., CO2 to syngas) in the counter chamber can be coupled with a targeted reaction to reduce the energy loss during electrolysis (Figure ). In summary, we highlight the potential of immobilizing molecular catalysts, especially organometallic catalysts, onto electrodes to afford a potent catalytic material to interconvert electrical and chemical energy. Such a hybrid system is constructed from a modified electrically addressable surface and metal complexes via a handful of immobilization methods. Effects on electron transfer rate, activity enhancement, product selectivity, and catalyst lifetime are discussed. Implications of functional groups, external electric field, and solvent are emphasized for catalyst optimization. The easy, ready, and precise access to electric current provides an excellent avenue toward temporal control and redox altering of a catalyst's behavior. Implementing orthogonal chemistry with electrochemical transformations represents a future direction of accomplishing complicated syntheses from simple building blocks such as CO2. Overall, the surface functionalization of molecular compounds on an electrically addressable surface heralds a new paradigm in designing and conducting chemical transformations.