High-density graft films bearing ferrocene (Fc) moieties were fabricated on quartz and indium tin oxide (ITO) substrates by surface-initiated atom transfer radical polymerization (ATRP). The thickness of the film increased with the increase in the molecular weight of the polymer. We successfully observed quantitative electrochemical redox signals on the ITO substrates coated with a graft polymer. The cyclic voltammograms showed that all ferrocene moieties were electrochemically active.