The complexing ability of thin poly(3-pyrrol-1-ylpropyl)malonic acid films coated onto glassy carbon disc electrode surfaces was evaluated towards Pb(II) and Cu(II) ions, using the chemical preconcentration-anodic stripping method. The affinity of these metal cations for the complexing film modified electrodes and their maximal surface coverage rate could be evaluated from a Langmuir isotherm model coupled to the chemical preconcentration-anodic stripping technique. Isothermal studies conducted between 293 and 308 K allowed to estimate enthalpy and entropy variations associated to the metal sorption, which expectedly proved to fit chemisorption processes. As judged from the estimated binding constants, Pb(II) ions turned out to present a higher affinity for the functionalized surface than the smaller Cu(II) species. The mobilization of a higher number of malonic acid units per metal cation upon complexation of Pb(II), as compared to Cu(II), is however believed to account for the estimated lower Pb(II) surface coverage. The combination of the Langmuir isotherm model to the chemical preconcentration-anodic stripping technique is thus revealed to be an efficient method to characterize the complexing ability of complexing film electrode surface. (c) 2007 Elsevier B.V. All rights reserved.