Electron transfer behavior at polyoxometalate-adsorbed alkanethiol self-assembled monolayers

► Polyoxometalate ions adsorb on the surface of alkanethiol self-assembled monolayers. ► POM adsorption on SAM forms a composite organic-inorganic hybrid layer. ► The electron transfer behavior at SAM can be controlled by the adsorption of POM. ► The chain length of SAM and charge of POM controls the electron transfer features.