The lipid matrix present in the human stratum corneum (the thin, uppermost layer of the skin) is considered to play a crucial role ill the skin barrier function. The lipid matrix consists of ceramides, cholesterol, and free fatty acids. The 13 nm lamellar phase present in the lipid matrix of the stratum corneum is very characteristic and plays an important role in the skin barrier function. One subclass of ceramides with a linoleic acid linked to a very long acyl (referred to as EOS) plays a crucial role in the formation of the 13 nm lamellar phase. In this article, we focus on the lipid phase behavior of EOS mixed with cholesterol or with cholesterol and free fatty acids. Our studies reveal that an equimolar ratio of EOS, cholesterol, and free fatty acids forms a lamellar phase with a very long repeat distance of approximately 14.7 nm. This phase exhibits exceptional behavior in that in the thermotropic response the fatty acid chains and the ceramide chains undergo an order-disorder transition in different. temperature ranges while part of the hydrocarbon chains of ceramides and fatty acids are mixing in the orthorhombic lattice. On the basis of these observations, a Molecular model for the 14.7 nm phase has been proposed in which the lipids are organized in it lamellar phase with three different lipid layers in a symmetric unit cell.