AbstractThe free sterols, the sterol esters and the sterol glycosides of the crude sunflower oil as well as those of the technical lecithin, the pitch and the deodorizer distillate of the latter oil were isolated by preparative TLC. The nature of sterols contained in the isolated sterol derivatives was elucidated by GLC and combined GLC‐MS.Major sterols of all examined sterol fractions are sitosterol, campesterol and stigmasterol, the amount of sitosterol being prevalent. Unknown sterol with a molecular weight of 428is present in sterols of the crude oil and the deodorizer distillate. Sterols of the deodorizer distillate contain an unknown sterol with a molecular weight of 430. Stigmasterol is present in the sterol fraction of the deodorizer distillate in high amounts. It was established that Δ7‐sterols of the crude oil occur only in esterified form.The hydrolysis of the sterol derivatives in acid medium leads to dehydration products known as steroid dienes and disteroid ethers. Hydrolysis without dehydration was achieved by enzyme preparations.Some sterols of the crude oil were esterified with the same higher fatty acids contained in the glycerides of the sunflower