The electroreduction of the peroxodisulfate anions on the electrochemically polished (EP) Cd(0 0 0 1), Bi(1 1 1) and Bi (01(1) over bar) planes has been studied by cyclic voltammetry, rotating disc electrode and impedance methods. The rate constant values of the heterogeneous electroreduction reaction of the S2O82- anion on the EP Cd(0 0 0 1) and Bi(h k l) planes dependent on electrode polarisation and base electrolyte concentration have been calculated. The values of apparent transfer coefficient alpha(app) corrected for the double layer effect (alpha(app) <= 0.15) only very weakly depend on the electrode potential and base electrolyte concentration. The very low values of the charge transfer coefficient for S2O82- electroreduction show that the activationless charge transfer mechanism is valid for EP Cd(0 0 0 1) and EP Bi(h k l) electrodes in various surface inactive base electrolyte solutions. This conclusion is in a good agreement with the theoretical models for the high hydrogen overvoltage metals based on the diabatic charge transfer mechanism from the metal to an ion [R.R. Nazmutdinov, D.V. Gluhov, O.A. Petrii, G.A. Tsirlina, G.N. Botikova, J. Electroanal. Chem. 552 (2003) 261]. (C) 2005 Elsevier B.V. All rights reserved.