The presence of mixed adsorption layers affects the mechanism and kinetics of irreversible Bi(III) ions electroreduction process in 2 mol.dm(-3 )chlorates(VII). Triton X-100 and Tween 80 change the dynamics of the catalytic activity of 6-mercaptopurine (6MP) on Bi(III) ions electroreduction with the tendency of inhibition. Above the critical micelle concentration of Triton X-100 and Tween 80, the irreversibility of Bi(III) ions electroreduction decrease to the size comparable to the irreversible reduction of BM) in 2 mol.dm(-3 )chlorates(VII) which can be associated with the electrode surface blocking by formed hemispherical surface micelles. It was proved that the unstable complexes of Bi - 6MP or mixed Bi - 6MP - TritonX-100 and Bi - 6MP - Tween 80 intermediating in electrons transfer, play a significant role in the multi-stage mechanism of the electrode process. The hydration shell and composition of active complexes change as well. The obtained regularities indicate that in this case confirmed changes in entropy are a decisive factor.