The Raman spectra of styrene and atactic polystyrene have been recorded at 85 and 225 K. As the temperature is lowered, all 42 vibrational modes of the styrene molecule were resolved including those normally of very low intensity in Raman scattering. A general increase in the intensity of all lines and in the number of overtones and combination bands was observed. The frequency of out-of-plane vibrational modes was increased due to increased steric hindrance, whereas the frequency of in-plane modes remained relatively stable. Of particular interest are 11 low frequency modes, most of which are believed to track low frequency benzene-vinyl torsional oscillations from gaseous styrene and are enhanced by the crystal field. Depolarization ratios were measured for styrene at 300 K and polystyrene at 300 and 85 K. We have confirmed that there is some correlation between very symmetric vibrational modes in styrene and atactic polystyrene and strong polarization (ρV<0.2), and between very asymmetric vibrational modes and strong depolarization (ρV⩾0.5). Because of the polycrystalline nature of solid styrene it was not possible to measure depolarization ratios in this case. There is no significant change in the spectra of atactic polystyrene on lowering its temperature.