For the first time, electroactive poly(melamine) film has been prepared and evaluated to function as a matrix to immobilize spherical copper nanoclusters and also as a ligand to form a copper complex with enhanced electrocatalytic activity. This is a simple two-step process that involves first polymerization of melamine on a screen-printed carbon electrode followed by electrodeposition of copper without using harmful and environmentally toxic chemicals. It is remarkable that this electrode can electrocatalytically reduce H2O2 at approximately -0.2 V versus Ag/AgCl in pH 7 PBS and possesses superior stability in amperometric analysis of H2O2 under the continuous wall-jet flow of 1 mM of H2O2 for more than 5 h. Most importantly, we have demonstrated that the as-prepared copper-poly(melamine)-modified electrode can solve the setbacks of copper-based H2O2 sensors reported so far. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1639-1646