SummaryFrom polyglycerol samples, pure standards of tri and tetraglycerol were obtained using a column chromatographic technique. Polyglycerols were derivatised to trimethyl silyl derivatives to obtain gas chromatographic identification of all linear, branched and cyclic diglycerol isomers and all linear and branched triglycerols. Moreover, quantitative gas chromatographic analysis of the di-, tri-and tetraglycerol content of a polyglycerol sample was developed. Finally a method to characterise, on a quantitative basis, the polyglycerol content ofpolyglycerol fatty acid esters was developed. It consisted of saponifying the esters, without affecting the degree of polymerisation of the polyglycerols, followed by gas chromatographic analysis of the isolated polyglycerol fraction.