The IR spectra of mixtures of methoxyflurane and dimethyl ether are studied with the help of FTIR cryospectroscopy in liquefied Xe. The region of CH₃ and CH stretching vibrations is examined taking into account the Fermi resonance effect. Comparative analysis of the experimental data and results of ab initio calculations show that the Cl₂CH group of methoxyflurane is involved in complex formation which is stabilized by H-bond between H atom of this group and O atom of dimethyl ether predominantly.