The thermal degradation products of the 7α- and 7β-cholesteryl 3β-acetate hydroperoxides obtained by thermal oxidation of cholesteryl 3β-acetate are reported and discussed. The hydroperoxides were degraded in both the vapour and condensed phases. The main components identified were 7-ketocholesteryl 3β-acetate, 7α- and 7β-hydroxycholesteryl 3β-acetates and the products generated from the loss of the hydroperoxide group and/or of acetic acid. Remarkable is the finding of the epoxy-hydroxy derivatives of cholesteryl acetate among the degradation products.