The thermotropic phase behaviour and structural organisation of ceramide N-linoeoyl-phytosphingosine (ceramide 3A) is investigated by means of differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). Its polymorphism and structural properties are compared with two ceramides of the type III class with various hydrocarbon chain saturation degrees. After hydration the main phase transition temperature of ceramide 3A is found at 76 °C with a phase transition enthalpy of +29 kJ mol⁻¹. Analysing the frequency of methylene stretching vibrations (by infrared spectroscopy) reveals that the fluidity (amount of trans–gauche isomers) is strongly increased for ceramide 3A compared to its stearoyl ceramide type III analogue. After lipid hydration, the acyl chains of all investigated phytosphingosine ceramides of type III adopt a hexagonal-like chain packing. The amide I and amide II vibrations are quite sensitive to the phase transition of the ceramide. The corresponding band analysis reveals strong inter- and intramolecular hydrogen bonds between the amide and hydroxyl groups in the ceramide head groups. The H-bonding network and conformation of the head group of ceramide 3A is only slightly influenced by hydration. The water penetration capacity of ceramide 3A is, however, considerably larger compared to other phytosphingosine derivatives. The structural and organisational properties of ceramides of type III class are discussed with respect to their physiological relevancies for the stratum corneum lipid barrier property of the skin.