The effect of hydration on the structure and molecular orientation of multibilayers of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), cast on a germanium plate, was studied by means of polarized Fourier transform infrared (FT-IR)-attenuated total reflection spectroscopy. Compared with the dry state, the antisymmetric and symmetric CH2 stretching bands of fully hydrated DMPC in the liquid-crystalline state were shifted to the higher frequency side, indicating the increase in the number of the gauche conformers. However, the dichroism of these bands revealed that the hydrocarbon chains of DMPC were still ordered and titled. The absorption bands of the glycerol ester, phosphoryl, and choline groups were broadened upon hydration, suggesting the activation of the librational or torsional motion. Furthermore, the dichroism of the polar head group bands of DMPC indicated that these groups retained a slight orientation even in the fully hydrated and fluid multibilayers.