A Keggin-type POM is attached to gold or glassy carbon surfaces by electro(chemical) or peptidic coupling. In addition to demonstrating the robust attachment of the POMs (by electrochemistry, XPS, and IRRAS), the surface concentration, layer thickness, and rate constant for electron transfer from the surface to the POMs have been measured. The use of such complementary techniques is mandatory to characterize the modified electrodes properly. Whatever the grafting method, experimental conditions are found to allow monolayer or submonolayer coverage. Besides covalently grafted species, additional electrostatically bonded POMs are present in the film. Cathodic polarization allows removing them to get a grafted film that is stable with time and potential, which is a requirement in the design of molecular memories.