The presence of mixed 6-thioguanine-nonionic surfactant adsorption layers affects the mechanism and kinetics of the irreversible Bi(III) ion electroreduction process in chlorates(VII). Tween 80 and Triton X-100 change the dynamics of the catalytic effects of 6-thioguanine on Bi(III) ion electroreduction with the tendency of inhibition. The mechanism of catalytic activity of 6thioguanine is associated with formation of complexes under specific conditions which exist on the electrode surface. The effects of both 6TG and suitable surfactant mixture on the first electron transfer are much greater than those on the transition of other electrons. The Bi-6TG type complex plays the main role in the Bi-6-thioguanine-Tween 80 or Bi-6-thioguanine-Triton X-100 systems, as 6-thioguanine dominates in the formation of adsorption equilibria of the studied mixtures.