State-of-the-art in the field of quantum chemical modelling of the heterogeneous electron transfer processes is reviewed. Novel approaches originating from interplay between quantum chemistry and modern theory of charge transfer ale discussed and illustrated by recent results on the calculation of relevant kinetic parameters for various electrochemical systems. Emphasis is made on the modelling of the inner-sphere reorganization and the works of approach, as well as on the consideration of reaction layer as an orientational ensemble of reagents. Recent approaches to the estimation of electronic transmission coefficient are analyzed. A possibility to employ traditional phenomenological theory to the analysis of experimental data is re-examined in the framework of microscopic treatment.