The matrix-isolation infrared spectrum of a thermally evaporated ionic liquid, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([Emim][OTf]), was measured by FTIR spectroscopy and analyzed with the aid of DFT calculations. The main chemical species in the observed IR spectrum was mainly identified as the 1:1 cation-anion pair, which corresponds to the second stable ion-pair structure bonded through five hydrogen bonds between three O atoms of the anion side and four H atoms of the cation.