Conducting polypyrrole membranes were deposited on glassy carbon electrodes by electropolymerizing pyrrole in the presence of Eriochrome Blue-Black B (EBB) as the counter anion. The electrodes were then subjected to several oxidation/reduction potential steps in pure silver nitrate solution for successive accumulation/stripping of silver species. This electrochemically mediated doping/templating generated selective recognition elements in the EBBIPPy film for silver ions. The resulting sensor exhibited a considerable enhancement in the potentiometric and voltammetric response characteristics: extending the linear dynamic range and lowering the detection limit. In the potentiometric mode, the sensor showed highly reproducible response with a Nernstian slope of 58.5 +/- 0.3 mV per decade of Ag+ activity over a linear range spanning seven orders of magnitude (1 x 10(-8) to 1 x 10(-1) M Ag+), with a detection limit of similar to 6 x 10(-9) M. The electrodes demonstrated high selectivity over a large number of cations including alkali, alkaline earth and several transition and heavy metal ions, and could be used over a wide pH range of 1-8.5. The EBB/PPy modified electrode was also used for preconcentration and differential pulse anodic stripping voltammetric (DPASV) measurements. The DPASV peak current was dependent on the concentration of Ag+ over the range 3 x 10(-10) to 1 X 10(-4) M. The presence of 1000-fold excess of Cd2+, Cu2+, Cr3+, Co2+, Mn2+, Fe2+, Fe2+, Ni2+ and Pb2+ can be tolerated in the determination of silver ion. (c) 2006 Elsevier Ltd. All rights reserved.