The approach to the calculation of the activation energy of electrochemical charge transfer is considered for systems characterized by asymmetry of inner-sphere reorganization (i.e. by the difference in inner-sphere reorganization energies for direct and reverse reactions). Model calculations are carried out and the region of parameters is evaluated for which the effect is pronounced. A quantum-chemical analysis of inner-sphere reorganization is presented for four cobalt and chromium chelate aminocarboxylate complexes and the corresponding contribution to activation energy is discussed in connection with the difference in rate constants.