The Raman spectrum of an oriented single crystal of CaSO4∙2H2O has been recorded from 20 to 3600 cm−1 at 300 °K and 77 °K using polarized laser excitation. The symmetries of the observed Raman lines have been determined and the spectrum has been analyzed in terms of external lattice vibrations, internal vibrations of the SO4 and H2O groups, hydrogen bond vibrations, and combinations of these vibrations. The translatory and rotatory lattice modes of the H2O molecules have been identified and the latter have been correlated with the principal moments of inertia of the water molecule. The hydrogen bond vibration was observed at 210 cm−1 at 300 °K and 217 cm−1 at 77 °K. The assignments of the internal modes were found to be consistent with the results of previous workers. Several overtone and combination frequencies were observed, especially in the region of the ν1 and ν3 vibrations of H2O.