Raman spectra of aqueous dispersions of 1,2-dipalmitoyl-phosphatidylcholine (DPPC) have been measured as a function of pressure (up to 46 kbar) for samples incubated at 2°C and for nonincubated DPPC samples subjected to equally high pressure. The nature of the transition from the GII gel phase of the hydrated lipid into the subgel phase on incubation is entirely different from that of the transition from the GII gel phase into the GIII gel phase of the nonincubated lipid. The GIII gel phase has a monoclinic interchain packing, while the subgel phase exhibits a triclinic interchain structure. It is shown that pressure cannot induce the transition from the GII gel phase to the subgel phase; however, it does stabilize the subgel phase above the subtransition temperature. The mechanism for the formation of the subgel phase and the complex phase behavior of the gel phase of DPPC are rationalized in terms of the dynamic properties of the acyl chains of the lipid molecule.