The FTIR spectra of fluoroform + methyl fluoride mixtures trapped in argon and nitrogen matrices are studied at T~10–30 K. Spectroscopic changes observed in the region of the CH stretching mode of fluoroform are typical for weak blue shifting H – bonds of C–H⋯F type. The degeneracy lifting effect found on E – type bands of fluoroform interacted with methyl fluoride suggests the complex formation of a nonlinear form. The experimental results are confirmed by ab initio calculations of fluoroform + methyl fluoride based on the second order Møller-Plesset theory of perturbations utilizing advanced basis set. Nonlinear complexes are stabilized by the basic C–H⋯F interaction and additionally by van der Waals-type C–D⋯F–C contacts between deuterated methyl fluoride and fluoroform.