Summary: 2H NMR solid‐state spectra of aromatic molecules (benzene, toluene, chlorobenzene, naphthalene) included in clathrate phases of syndiotactic polystyrene (s‐PS) or absorbed in the amorphous phase of s‐PS, have been recorded and analyzed for a broad range of temperature (230–360 K). The dynamic processes accessible to aromatic molecules absorbed in s‐PS clathrate phases are essentially temperature independent for the whole temperature range under investigation. Moreover, the molecular re‐orientations reflected in the NMR line‐shapes are similar to those accessible to the same molecules when absorbed in polystyrene amorphous phase at temperatures substantially lower than the polymer glass transition temperature. A simulation procedure for 2H NMR line‐shape analysis has been used to establish models for the dynamic processes of the different aromatic guest molecules.Solid‐state 2H NMR spectrum of naphtalene‐d8 in the amorphous phase of a semi‐crystalline s‐PS film (A), in the s‐PS clathrate phase (B) and the simulated spectrum for a static CD bond (C).magnified imageSolid‐state 2H NMR spectrum of naphtalene‐d8 in the amorphous phase of a semi‐crystalline s‐PS film (A), in the s‐PS clathrate phase (B) and the simulated spectrum for a static CD bond (C).