Poly(pyrrole-malonate) films have been synthesised by oxidative electropolymerisation of the new pyrrole-malonic acid monomer 1. Poly1 films partition strongly the hexaaamine ruthenium cations from aqueous electrolytes, allowing an estimation of the acidity constant values of poly1 from cyclic voltammetry data. The complexation of copper(II) cations in this chelating polymer was evidenced by FT-IR and electrochemical experiments. Electroreduction of the complexed poly1-Cu(II) leads to the precipitation of copper metal in the polymer film.