In this work, we have carried out a comprehensive characterization of the vibrational spectroscopy of the non-planar molecule thianthrene. The combination of infrared, Raman and inelastic neutron scattering spectroscopies is highly complementary and allows all of the modes to be observed. Periodic density-functional theory calculations have provided unambiguous assignments of the spectra. The literature states that C–S stretch modes occur in the 600–800 cm
−1
range. We find that while there are modes that involve sulfur motion in this region, this is a consequence of motion in the
ortho
-phenylene rings. The modes that are driven by the C–S stretches are found in the ~400–500 cm
−1
range. The C–S–C bending modes occur in the 200–300 cm
−1
range; these have not been previously characterized.