Attempts of describing metal/solution interfaces on the basis of cluster model and quantum chemical methods of different levels, made during the past decade, are surveyed and critically discussed. Even relatively small clusters modelling of a metal surface are shown to be an effective implement to handle fundamental problems of the double layer theory. Liophilicity of metals, dissociative water chemisorption, adsorption of hydrated ions and the contribution of a metal electrode to the interfacial capacity are topics of primary attention in this paper. In order to elaborate a new molecular model for a charged electrode surface, we consider in detail specific problems of the quantum chemical approaches and possible ways to surmount these. To supplement the picture of the state-of-the-art in the area of microscopical modelling under consideration, we report some original results concerning the study of hydrophilicity of low-index silver faces. The interplay between traditional electrochemical model concepts and "quantum chemical" language is illustrated by a great deal of both db initio and semi-empirical calculations.