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An ionic liquid (IL) BMIGaCl 4 was prepared by directly mixing GaCl 3 and 1-methyl-3-butylimidazolium chloride with molar ratio of 1/1 under argon atmosphere. The densities and surface tensions of this pure ionic liquid were determined in the temperature range of 268.15 to (338.15±0.1) K. A new theoretical model of ionic liquids, an interstice model, was applied to calculate the thermal expansion coefficient of IL BMIGaCl 4 , α, and the magnitude order of its value calculated by the theory was the same as experimental one. Both Raman scattering and ab initio calculations indicate that 4 GaCl-is the only species containing Ga in the ionic liquid BMIGaCl 4 .