The measurements concerning the process of the electroreduction of Bi(III) ions in the presence of 6–thioguanine (6TG) and Triton X-100 as well as Tween 80 in the 2 mol·dm-3 chlorates(VII) demonstrate a dependence of the process rate on temperature. The applied electrochemical techniques (DC polarography, cyclic and SWV voltammetry) allowed to determine the kinetic and thermodynamic parameters as well as their correlation with changes in kinetics of the electrode process. The catalytic activity of 6TG was confirmed by the decrease of overall enthalpies of activation. Different values of ∆H^≠ and ∆S^0 for Bi(III) electroreduction in the presence of 6–thioguanine as well as Triton X-100 and Tween 80 suggest changes in kinetics of the electrode process towards inhibition.