Simultaneous time-resolved small-angle and wide-angle X-ray scattering has been used in the study of the isothermal crystallization behavior, after quenching, of triacylglycerols (TAG) with 18 carbons in the hydrocarbon chains. Saturated, unsaturated TAG, their blends and mixed saturated/unsaturated TAG were studied. The mixed saturated/unsaturated TAG and their blends form an a 2 -phase with a longitudinal packing different from two-chain and three-chain packings, which distinguishes them from the other fats. The unstable a 2 -phase, observed at the initial stage of crystallization of mixed saturated/unsaturated TAG, is classified as a transient mesophase. Two dimeric units proposed for a structural model of the a 2 -phase have been used to describe the structural organization of TAG molecules in the liquid state.