The electrodeposition of copper into ion-exchange materials with different ionogenic groups is studied. We have worked out that the discharge of copper counterions in an ion-exchange matrix is characterized by a cathodic overvoltage that is higher than the overvoltage of the same process on a graphite substrate by 0.08 V, which is most probably connected with a limited mobility of counterions localized at ionogenic groups. It has been observed microscopically that the process of deposition begins at the graphite substrate/ion exchanger interface and passes into the volume of a polymeric matrix with the filling of nanodimensional pores by copper. Preliminary doping of the ion exchanger by silver leads to the jump of the deposition current of copper counterions that is caused by the appearance of sufficient electron conductivity of the doped polymeric matrix. The data of the local X-ray spectral microanalysis confirm the regular deposition of copper into the volume of an ion exchanger grain doped by silver. (c) 2007 Elsevier Ltd. All rights reserved.