Abstract Raman and far-IR studies of hexamethylbenzene (HMB) low temperature crystalline phases (neat and isotopic mixed) are presented. The Raman phonon spectrum changes drastically during the λ-phase transition. Site splittings on two intramolecular modes of HMB- h 18 (but on only one corresponding HMB- d 18 mode) are observed in the room temperature phase (phase II) spectrum. These splittings disappear in the lower temperature phase (phase III). The methyl torsional bands are identified and a significant shift is observed for them during the phase transition. Also, while the λ-phase transition takes place at 113°K (± 2°K) for HMB- h 18 crystal, the transition temperature is 133°K (± 2°K) for HMB- d 18. Our results suggest that (for phonon interactions) the symmetry in phase Ill is close to D 3d and reduces to C i in phase II. Furthermore, the results support the mechanism of phase transition which involves a tilting of the methyl groups out of the benzene ring.