The phase behaviour of 1,2-distearoylphosphatidylethanolamine in glycerol has been examined using differential scanning calorimetry and real-time synchrotron X-ray diffraction methods. Dry phospholipid and phospholipid dispersed in glycerol over the concentration range 2.4%–90% (w/w) was equilibrated for 30 min at 20° C and thermal and structural parameters on the temperature range 60° C to 110° C recorded during an initial heating and subsequent reheating. The characteristic feature of the initial heating scan was a direct lamellar crystalline to inverted hexagonal phase transition. In the subsequent cooling scan a lamellar gel structure was formed from the non-lamellar phase which transformed, on reheating, to a lamellar crystalline phase in which the acyl chain packing was tilted with respect to the bilayer plane. The mechanism of the formation of the two crystalline phases was examined in the context of a relaxation model, where the liquid-crystal phase below the transition temperature from lamellar crystalline phase is metastable. A binary phase diagram over the temperature range 60° C to 110° C has been constructed.