in this work, the ion exchange characteristics of poly(butyl viologen) (PBV) thin films on a platinum electrode has been investigated by cyclic voltammetric (CV) scans. Since ferrocyanide anions (Fe(CN)6(4-)) were added during the polymerization of the PBV thin-film for its stability, Fe(CN)64- could form charge transfer complex with monomer and co-deposited with polymer. Scanning electrochemical microscopy (SECM) was used to probe the released Fe(CN)(6)(4-) ions from PBV film with Os(bpy)(3)Cl-2 as a mediator for the approaching process in 0.5 M KCl medium. Mass changes during the redox process of the film were also monitored in-situ by electrochemical quartz crystal microbalance (EQCM). The ion exchange and transport behavior was observed during CV cycling of the film of the SECM and EQCM. The insertion and extraction of anions were found to be potential-dependence. Moreover, the decrease in tip current of released Fe(CN)(6)(4-) with increasing cycle number accounted for the ion exchange between Fe(CN)(6)(4-) and Cl- in the KCl electrolyte. However, the Fe(CN)(6)(4-)/Fe(CN)(6)(3-) redox couple was found to be highly stable between 0.0 and 0.5 V (vs. Ag/AgCl/saturated KCl) in the phosphate buffer solution. Therefore, the electrochemical property of Fe(CN)(6)(4-)/Fe(CN)(6)(3-) redox couple was studied at different scan rates using CV technique. The peak currents were directly proportional to the scan rate as predicted for a surface confined diffusionless system. The surface coverage (F) and the concentration of Fe(CN)(6)(4-) were determined to be 1.88 x 10(-8) mol/cm(2) and 0.641 mol/dm(3), respectively. By neglecting cations incorporation during redox reaction of the PBV film and also based on the results obtained from energy-dispersive X-ray spectroscopy for the films of as-deposited, reduced and oxidized states, an ion exchange mechanism was proposed. (c) 2008 Elsevier Ltd. All rights reserved.