The interactions between N,N-dimethylformamide (DMF) and fluoroform (CHF ₃) in the gas phase are studied with the help of FTIR spectroscopy. Temperature changes observed in the region of the CO stretching mode of DMF suggest a weak complex formation that results in a red wavenumber shift of the ν(CO) band. Series of van Hoff plots obtained by means of temperature and concentration spectroscopic measurements give the energy of the complex formation ΔE ∼ −19.6 kJ/mol. Ab initio calculations performed at the MP2/6–311++G(df,pd) level are in good agreement with the experimental results.