The crude phospholipid mixture (PC70) forms a homogeneous gel with hexadecanol (HD) in water, whereas the purified lipid does not. The fact that the crude material PC70 can be utilized for homogeneous gel preparation suits the cosmetic industry very well from the viewpoint of cost performance. In order to clarify the mechanism of the gelation, we investigated the structures and physicochemical properties of the PC70/HD/water system by rheometry, freeze-fracture electron microscopy, differential scanning calorimetry (DSC) and synchrotron X-ray diffraction. Our results suggested that the gelation is induced by change in bilayer morphology from closed vesicles to sheet-like structures with open edges covered by minor lipid components that are stiffened due to intercalation of HD molecules between phospholipids. The morphological change may give rise to homogeneous distribution of the bilayer sheets throughout the solution and formation of water continuum that may work as a network in the gel. (C) 2012 Elsevier Inc. All rights reserved.