The crystal structure of [C(n)mim]NTf2 (n = 2, 4, 6) was studied for the first time simultaneously by X-ray diffraction method and IR spectroscopy. The temperature-dependent IR spectrum for crystalline [C(4)mim]NTf2 was demonstrated to correlate with both the X-ray data and the calorimetric results obtained earlier. Therefore, it was found that IR spectroscopy is able to establish the correspondence between the X-ray and the calorimetric data ill this case. The joint use of X-ray diffraction, IR spectroscopy, and quantum-chemical calculations allowed us to determine the structure of all [C(2)mim]NTf2 crystalline modifications obtained earlier by adiabatic calorimetry measurements. Thus, a new approach for the future identification of ionic liquid crystal Structure by use of temperature-dependent infrared spectroscopy is suggested and justified.