AbstractThe fatty acids at the sn‐2 position and the sterol composition of cocoa butter and three common cocoa butter equivalents (CBE), namely Coberine, Choclin and Calvetta, were studied comparatively, in order to develop a sensitive method for detecting CBE in chocolate. Differences observed in the composition of saturated fatty acids at position‐sn‐2 present some interest in detecting CBE in chocolate. Differences found in 4‐desmethyl and 4‐methylsterol compositions, although quite significant, did not present any practical interest because of the relatively small amounts present in CBE. The 4,4′‐dimethylsterol or triterpene alcohol fraction was found to have a potential for determining CBE in chocolate. Thus, the triterpene alcohols of Coberine were further fractionated on argentation thin layer chromatography (TLC) and analyzed by gas liquid chromatography (GLC) and gas chromatography‐mass spectrometry (GC‐MS). α‐Amyrin was found in 48.2% of the triterpene alcohols of Coberine and was absent from cocoa butter. Cycloartenol, the main 4,4′‐dimethylsterol of cocoa butter, and α‐amyrin were well resolved on an OV‐17 glass capillary column.