Cu(II)-exchanged fuller's earth was prepared by ion-exchanging Ca2+ ions which are present within the interlayer of fuller's earth with Cu(II)ions by the solution-phase ion-exchange process. Pyrrole was introduced into Cu(II)-exchanged fuller's earth to spontaneously polymerize to within the interlayer to result in a nanocomposite of Cu(I)–polypyrrole–fuller's earth where both Cu(I) and polypyrrole occupy within the interlayer spaces of fuller's earth. The nanomaterial [Cu(I)–PPY–FE] has been fully characterized with X-ray diffraction studies, FTIR spectroscopy, DC polarisation test with both blocking stainless steel and non-blocking copper electrodes. The material is found to be a mixed conductor whose ionic mobility is 1.5 times faster than electronic mobility. DC polarisation studies also clearly revealed that the mobile ionic species in this material to be cuprous ions. AC impedance studies have been carried out with blocking stainless steel electrodes at different applied potentials. The necessary theoretical background to explain AC impedance results is also provided and the results obtained agree very well with the corresponding data obtained by other mutually independent methods. The electronic conductivities are around 3.0×10−4 Scm−1 and the ionic conductivities are around 9.0×10−3 Scm−1. The material may find applications in semi-fuel cells such as air–metal batteries.