With the help of the polarization curves method (E-lgIa) there are investigated the anode processes at Co2O3 anode deposition together with the doping additives – nickel (NiO, Ni2O3) and chromium (Cr2O3) oxides at the electrolysis from the mixed sulfate solutions. The possible mechanisms of these processes interconnection with nucleation and crystal growth of binary oxide compounds of Co-Ni and Co-Cr and crystal structure formation of anode deposits are considered.