Melanin-modified highly oriented pyrolytic graphite (HOPG) surfaces have been prepared by a simple electrochemical method from synthetic eumelanin-containing aqueous Solutions. The melanin film turns the chemically inert HOPG surface into a highly active surface able to bind metallic cations. Iron-melanin-modified HOPG surfaces catalyze the hydrogen peroxide electroreduction. These results are interesting for applications in electrocatalysis, electroanalysis, and also as biomimetic systems for studying melanin interactions with nanoparticles and metallic cation-containing drugs. (c) 2008 Elsevier Ltd. All rights reserved.