Vibrational Raman spectra of polycrystalline 1,2-dipalmitoyl phosphatidylcholine-d9 (fully deuterated choline methyl groups) and 1,2-dipalmitoyl phosphatidylcholine-d62 (fully deuterated acyl chains) were recorded in the 3050- 2800, 2250-2050 and 1800-700 cm-1 regions. The fundamental vibrational modes were assigned primarily on the basis of isotopic frequency shift ratios, group frequency correlations and comparisons with specific model compounds. Since deuterium-substituted lipids provide well-isolated spectral probes, particularly in the carbon-deuterium stretching region, the dependence of the 2250-2050 cm-1 region on lipid phase was examined for the dipalmitoyl phosphatidylcholine-d62 species. The methylene CD2 deformation and twisting modes at 984 and 919 cm-1, respectively, also exhibit intense, isolated vibrational transitions which should prove useful for monitoring molecular order in mixed dueterated and undeuterated lipid systems. Except for the relatively weak choline methyl C-D and C-H stretching modes, the spectrum of 1,2-dipalmitoyl phosphatidylcholine-d9 is not distinguishable from that of the undeuterated system. For both the d9 and undeuterated species, the vibrational modes associated with the lipid head group region are sensitive to slight hydration.