The ionic and electronic conductivities of poly (acrylonitrile) films (PAN films) and of films which contained salts of copper (Cu-PAN films) have been investigated. The conductivities in both types of film (10−8 S cm−1 and 10−3 S cm−1, respectively) were predominantly due to ionic species. PAN films which possessed pendant amino moieties (PANf films) were treated with reducing copper-and sulphur-containing solutions to obtain films with surface electronic conductivities as high as 10−3 S cm−1. The surface morphologies of the films were investigated by electron microscopy and the natures of the conducting species are discussed.