The phenomenon of the decrease in the accelerating action of multicharged cations on the electroreduction of anions with increasing negative charge on the mercury electrode and with increasing concentration of KCI is investigated for inorganic cations of different size (K+, Ba2+, Ca2+, La2+, Lu3+, Y3+). This decrease for the electroreduction of anions of the first group is explained within the framework of the slow discharge theory in combination with the diffuse-layer model, considering the existence of two planes of the closest approach of cations and anions to the electrode surface and the decrease of the dielectric constant in the space between these planes compared with its value in the bulk solution. The psi(1) potentials at the center of the activated complex are calculated for different solution compositions in the presence of multicharged cations. This gives an opportunity to construct the corrected Tafel plots with the corresponding psi(1) potentials. It is shown that the effect of M3+ cations on the electroreduction of anions of the second group is connected with donor properties of water molecules in the hydrated spheres of these cations.