The results on the modelling of molecular interactions, supramolecular organization and physicochemical properties of halogenated hydrocarbon mixtures with organic solvents are presented. The mixtures both with negative deviation from ideality, such as propanone-trichloromethane, dimethylsulfoxide (DMSO)-trichloromethane and positive one (tetrachloromethane-methanol, trichloromethane-methanol, trichloromethane-ethanol) has been studied. The models of the aggregation of mixtures investigated due to specific intermolecular interactions are proposed. The thermodynamic characteristics of aggregation (constants of equilibrium, Gibbs energy, enthalpy and entropy) and structural parameters of aggregates have been determined. The manifestations of the supramolecular ordering on the physicochemical properties of the mixture are discussed. (C) 2003 Elsevier Science B.V. All rights reserved.