Cathodic electrografting of poly(2-chloropropionate ethyl acrylate) (poly[cPEA]) onto steel followed by the styrene grafting-from by atom transfer radical polymerization (ATRP) is an efficient strategy to impart strong adhesion to polystyrene films onto the electrically conductive substrate. Electrografting of poly(cPEA) chains at an appropriate potential and persistence of the activated chloride in the grafted chains were confirmed by XPS. Polystyrene deposition by ATRP with a ruthenium-based catalyst was analyzed by scanning electron microscopy and Raman spectroscopy. Adhesion of the polystyrene layer to the substrate is so strong that it cannot be detached by standard Scotch brand tapes. Moreover, local thermal analysis showed a loss of mobility for the PS chains tethered at the surface.