Silver ions (Ag(I)) were preconcentrated efficiently at open circuit from aqueous silver nitrate solution into polybenzidine (poly-Bz) film electrodes. The poly-Bz films were electrodeposited by means of cyclic voltammetry from benzidine (Bz) in acidic aqueous solutions. It was found that preconcentration of Ag(I) ions into the film is highly dependent on the pH, being more favored at neutral pH, that is, when the nitrogen in imine-amine groups in the polymer chain are not protonated. Under these conditions the Ag(I) ions do not compete with the H+ ions for the same site within the film. A simple diffusion model is assumed to explain the incorporation of Ag(I) ion into the poly-Bz electrodes. The distribution of the Ag(I) ion between the solution and film was established and a probable analytical application given. (C) 2000 Elsevier Science B.V. All rights reserved.