AbstractVarious chromatographic techniques for isolation and separation of highly esterified sucrose polyesters (SPE) of olive oil are described. High‐performance size‐exclusion chromatography was used to check the purity of the samples, particularly to show that SPE were free from unreacted fatty acid methyl esters. Thin‐layer chromatography (TLC), Iatroscan TLC flame‐ionization detection (FID) and highperformance liquid chromatography (HPLC) on reversed‐phase were applied for separation of octa‐, hepta‐ and hexaesters of sucrose. Pure fractions from the total mixture, obtained by column chromatography, were identified by infrared and nuclear magnetic resonance spectroscopy. When necessary, specific reactions were applied; particularly, silylation and lead acetate‐dichlorofluorescein (in toluene) spray were used to ascertain the degee of esterification of sucrose. Finally, octa‐, hepta‐ and hexaesters of sucrose were quantitated by silica column chromatography, TLC/FID and HPLC on reversed‐phase.