The polarized Raman spectra and infrared absorption spectra of NiI, * 6H,O were measured in the 50-4000 cm-' region at low temperatures. Deuterated samples were a150 studied and gave results which were useful for hterpretation purposes. Satisfactory assignments of water internal and external modes and lattice vibrations were made. Tbe vibrational analysis, on the basis of which the assignments were made, was related to the D,, factor group; however, the symmetry of the Raman-active bands, as deduced from polarized spectra, suggests that for water librations the C,, factor group provides a better basis for interpretation.