The polymorphism of an homologous series of highly purified mixed triglycerides has been studied using powder and single crystal X-ray diffraction techniques, in conjunction with thermal analysis and infrared spectroscopy. From thermal analysis, three polymorphs were identified. Single crystals of the most stable polymorph were obtained for two members of the series, 2-acetodimyristin (14-2-14) and 2-acetodipalmitin (16-2-16). Their unit-cell and sub-cell dimensions were used to interpret the powder data, and to provide preliminary general information about the crystal packing for this polymorph. Of the two other polymorphs identified, the first one (obtained by rapid cooling of the melt) is disordered, and transforms on standing, to a second, unstable intermediate polymorph. Infrared spectroscopy showed that for at least two of the three polymorphs, the long chain acyl groups of the triglycerides are in a parallel packing arrangement.