The peculiarity of polypyrrole/sulphate (PPy/SO4) films redox behaviour has been investigated by cyclic voltammetry and electron probe microanalysis. The changes in PPy/SO4 film ionic composition during the redox process, especially the influence of electrolyte cations on its redox properties, were studied in detail. It was established that in the solutions of double charged metal- or bulky tetraalkylammonium cations the redox activity of PPy/SO4 film is suppressed, its mechanism is speculated on the basis of the film’s morphological peculiarity (compact structure), hydration radii and energy of moving ions, also the aggravations to effective charge balanced intermediate states during redox cycling are taken into account. In the case of tetraalkylammonium ions instead of the charge compensation problem the hydrophilic nature of PPy/SO4 film, and on the other hand the hydrophobicity of cations, causes additional kinetical aggravations or even suppression of film electroactivity.