SummaryIt is concluded from x‐ray diffraction, thermal curve, and enzymatic hydrolysis that the predominant glyceride of cocoa butter is 2‐oleoyl palmitoyl stearin (POS) instead of 2‐palmitoyl oleoyl stearin (OPS), the configuration which has been rather generally accepted. Accordingly it is suggested that a fully satisfactory cocoa butter extender should be largely of symmetrical, disaturated configuration since only thus is the characteristic beta‐3 form of cocoa butter likely to be preserved.An important aspect of this finding is that all disaturated vegetable glycerides which have been well characterized are of symmetrical, disaturated configuration. This not only supports the idea of the formation of specific glycerides in natural fats as opposed torandom fatty acid distribution but also points to some important common feature in vegetable glyceride metabolism.