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NMR and Raman spectroscopic methods have been used to study deuterated chloroform (ca. 10 mol%) with added pyridine (py), quinuclidine (Q) or triethylamine (Et 3 N) (0 – ca. 15 mol%) in cyclohexane solutions. In the Raman spectra of the CDCl 3 solutions new bands shifted to lower wavenumbers appear for the CCl and CD stretching vibrations when the above N-donor Lewis bases are added. These bands age ascribed to the formation of 1:1 hydrogen bonded complexes with CDCl 3 . A quantitative evaluation of the band areas, using the breathing mode of cyclohexane as internal standard, allowed relative molar scattering coefficients to he evaluated for the displaced CCl bands of the CDCl 3 hydrogen bonded species by fitting calculated to experimental concentrations. Equilibrium constants were then obtained for the 1:1 complex formations CDCl 3 + N-donor ⇌ CDCl 3 ·N-donor: K py = 0.8 ± 0.2, K Q = 0.8 ± 0.2, and K Et 3 N = 0.53 ± 0.05 dm 3 mol −1 . The NMR relaxation times of 2 D and 35 Cl for CDCl 3 have been measured and analyzed in terms of anisotropic rotational diffusion, in addition the perpendicular rotational diffusion constant of CDCl 3 in cyclohexane has been estimated from the Raman CD stretching band widths. Using the concentrations of the free and hydrogen bonded CDCl 3 species from the Raman experiment the rotational correlation times for the CDCl 3 ·N-donor complexes have been obtained.