Polycrystalline tetracalcium phosphate (TTCP), a material of considerable interest for human implantation due to its similarity to hydroxyapatite, was studied by means of Raman and FT-IR spectroscopy. The spectra were interpreted on the basis of group theoretical considerations. In addition, the setting reaction of a calcium phosphate cement (CPC) consisting of an equimolar mixture of TTCP and dicalcium phosphate (DCPA) was investigated by Raman spectroscopy. The band of the totally symmetric phosphate mode v1 of TTCP showed marked factor group splittings. The splitting components arose at coincident wave numbers in the IR and Raman spectra. This observation was in accordance with space group P2(1) (factor group C2(2), Z = 4). The characteristic splitting of v1 allowed the setting reaction of CPC to hydroxyapatite to be followed. According to the Raman spectroscopic results, considerable amounts of TTCP must be present at the sample surface after 24 h of setting in an aqueous environment.