A novel electrograft method of forming covalent bonds directly to silicon hydride or platinum surfaces has been demonstrated with the use of iodonium salt precursors. Initially, a silicon substrate is treated with a dilute hydrofluoric acid wash to ensure a hydride-passivated surface, which is immersed in a solution of iodonium salt dissolved in a solution of tetrabutylammonium tetrafluoroborate in acetonitrile. Grafting is accomplished by applying a negative bias to the silicon substrate. Directed assembly has been demonstrated with Pt substrates.