Water-alcohol solutions are widely used in pharmacy, food industry, engineering, etc. The study of their physical and chemical properties has a long history. Nevertheless, due to the complexity of these systems, there is still an interest in their research stimulated by the development of biochemistry in terms of the study and protection of the environment, global climate change, renewable energy resources and cosmochemistry. The purpose of the presented study is the quantum-chemical investigation of water clusters with methyl and ethyl alcohol molecules, as well as the modelling of concentration dependences of the excess molar volume of ethyl alcohol solution in water at different temperatures. Based on quantum-chemical calculations of paired and mixed complexes of water with methanol and ethanol, taking into account solvation effects, study reveals the formation of thermodynamically efficient complexes in liquid, in contrast to the ideal gas state, while in the mixture both individual solvated alcohol molecules and complexes will be in equilibrium. We noted a relative difference in the free energies of solvation of paired and mixed methanol and ethanol complexes. The paper proposes a technique for calculating the excess molar volume in water-alcohol mixtures by approximating the experimental dependences by Lejandre polynomials of the ninth degree. The calculation results showed high accuracy. Hence, continuous functions describe the dependences of the calculated coefficients of Lejandre polynomials on temperature.