It was first established that Bi(III) can be reduced by Ti(III) complexes in an autocatalytic mode and that the main features of the process can be interpreted in terms of pure electrochemical mechanisms. The electrochemical parameters of partial reaction coupling, which could be easily changed by means of the Bi(III) and Ti(III) ions complexation, govern the possibility of the process as well as its rate and the nature of the product formed (continuous film or stable sol). For the process to proceed it is necessary that not only the thermodynamic condition be met, but that the kinetic hindrances for the reductant oxidation be eliminated and these are realized when electroactive protonated Ti(III) complexonates are formed. The rate of Bi deposition onto the conductive surface in the acid medium is controlled by the partial reaction mixed current j(mix) and is independent of Delta E(dep) = E(Bi(III)/Bi) - E(Ti(IV)/Ti(III)), while the solution stability depends mainly on the Delta E(dep) and is independent of j(mix).