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The polymorphism and phase transitions of cocoa butter (CB) have been reexamined separately by differential scanning calorimetry (DSC) and X‐ray diffraction as a function of temperature (XRDT) at scanning rates between 0.1 to 5°C/min and 0.1 to 2°C/min, respectively. A new instrument, which allowed simultaneous DSC and XRDT recordings from the same sample by taking advantage of the high‐energy flux of a synchrotron, was employed for characterization of the intermediate phase transitions. These techniques allowed us to confirm the existence of the six polymorphic forms of CB (called I to VI) by in situ characterization of their formation in the DSC + XRDT sample holder. A detailed study of Form I structure led us to propose a liquid‐crystal organization in which some of the chains displayed sharp long‐spacing lines (d001=52.6±0.5 Å) and a β′ organization (4.19 and 3.77 Å), while the others remained unordered with broad scattering (maxima at about 112 and 36.5 Å). The organization of this liquid crystalline phase is compared to that of fat and oil liquids. This liquid crystalline phase progressively transformed on heating into a more stable phase (Form II, α type, d001=48.5±0.5 Å and short‐spacing at 4.22 Å). Form III was only observed in a sharp temperature domain through its specific short‐spacings. The existence of the six species has been essentially related to the crystallization of monounsaturated triacylglycerols (TAG), while trisaturated species were found partly solid‐soluble in these six polymorphic forms. An insoluble fraction crystallized independently of the polymorphism of the monounsaturated TAG in a separate phase with long‐spacings that were either of the α (49.6±0.5 Å) or β (44.2±0.5 Å) form. In mixture with Form V, this fraction melts and solubilizes in the liquid phase at 37.5°C. Isolation of these high‐melting crystals shows a melting point of about 50°C. High‐performance liquid chromatography analysis of this fraction confirmed an increase from 3.0 to 11.3% of saturated TAG and their association with part of the 1,3‐stearoyl‐2‐oleoylglycerol preferentially to 1‐palmitoyl‐2‐oleoyl‐3‐stearoylglycerol and (1,3‐palmitoyl‐2‐oleoylglycerol).

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