Metal electrodes such as Cu, Au, Ag play an essential role in electrochemical studies. The intrinsic electronic structure of the metal electrode determines the electrocatalytic activity of the system, while the desorption energy of active species on the surface can be modulated by polarizing the electrode surface based on calculations. In light of that, immobilization on the metal electrode surface was employed to modulate the catalytic activity. For example, Deng and coworkers triggered an electropolymerization of molecules to generate organic frameworks on the surface of a gold electrode, which created a compact interface enriched by amino groups. This non-covalent modification of the metal electrode surface resulted in higher CO production and selectivity than bare gold electrode under the same conditions. To increase the available anchoring sites on metal surfaces, pre-modifications of metal are commonly required accommodated modified molecular functionality. For example, a gold surface modified by alkanethiol groups with terminal azides was functionalized by a biomimetic molecular catalyst equipped with terminal alkynes via "click reaction".