In this paper, the influence of the side chain length of five ionic liquids (ILs): 1-methylimidazolium chloride ([C(0)mim][Cl]), 1,3-dimethylimidazolium chloride (([C(1)mim][Cl]), 1-ethyl-3-methylimidazolium chloride (([C(2)mim][Cl]), 1-butyl-3-methylimidazolium chloride (([C(4)mim][Cl]) and 1-hexyl-3methylimidazolium chloride (([C(6)mim][Cl]) on the interactions with ethylene glycol (EG) was studied. Based on the measurement of density and electrical conductivity of the ionic liquid + EG mixture in the temperature range (278.15-313.15) K, the values of apparent molar volume, standard partial molar volumes, apparent molar volume at infinite dilution, Masson's interaction coefficient, thermal expansion coefficient, limiting apparent molar expansibilities, Heppler's coefficient, ion association constants, thermodynamic parameters of ion-pair formation as well as diffusion coefficient was calculated. Experimental results were supported by molecular dynamic simulations. With the increase of the side chain length, from C(0)mim(+) to C(6)mim(+) cation, ion-dipole interactions on the solvation process decrease, and the influence of solvophobic solvation increases. Ionic liquids [C(0)mim][Cl] and [C1mim][Cl] show structure-breaker properties, [C(4)mim][Cl] and [C(6)mim][Cl] structure-making properties in EG solutions, while [C(2)mim][Cl] is borderline. The values of ion association constants in EG are higher than in water. The ion association process is spontaneous for all ionic liquids and entropy-driven.