Two O-bases and one N-base were studied in chloroform as well as in deuterochloroform solutions. Moreover, methanesulfonic acid, dimethylphosphinic acid, their tetrabutylammonium salts and their homoconjugated complexes were studied in an acetonitrile–chloroform mixture. The solutions were measured in the middle infrared region (MIR) at room temperature. The spectral data in the region of the stretching vibrations demonstrate the formation of CH⋯O and CH⋯N hydrogen bonds with relatively high stability. The interaction of chloroform with basic O-atoms and N-atoms is indicated by a broadened and slightly bathochromically shifted ν(CH) vibration band. Furthermore, a new transition at about 2500 cm −1 was observed, being very characteristic of hydrogen-bonded chloroform molecules. This new band is assigned to the 2δ(CH) vibration, intensified by Fermi resonance with the ν(CH) vibration. Obviously, the intensity of this band reflects the strength of the solvent interaction. This result is confirmed by results of the investigation of two acids, their respective salts and their homo-conjugated complexes.