Characterizing the interface involving covalently or noncovalently anchored molecular catalysts provides a comprehensive understanding of the hybrid system. Most organometallic complexes with redox-active metal centers or redox non-innocent functionalities can deliver electrochemical responses in cyclic voltammetry to display unique features. Besides electrochemical characterization, heavy elements and representative binding modes with the electrode surface can also be analyzed by spectroscopic techniques, such as UV-vis, IR spectroscopy, X-ray photoelectron spectroscopy, and can compensate for the lack of information in cyclic voltammetry experiments under some circumstances.