A liquid chromatographic method has been developed for the analysis of polyglycerol fatty esters and fatty ethers which are non-ionic surfactants. Two methods were compared using either octadecyl silica or porous graphitic carbon. The octadecyl silica system with a hydroorganic mobile phase enables to compare the hydrophobic behavior of the compounds. The porous graphitic carbon enables the separation of the diastereoisomers. Detection of these non-UV-absorbing compounds was achieved by evaporative light scattering detection. Identification of isomers was performed by mass spectrometry.