The phase behavior of a binary system constituted of purified 1,3-dicaproyl-2-stearoyl-sn-glycerol (CSC) and 1,2-dicaproyl-3-stearoyl-sn-glycerol (CCS) was investigated at a very slow (0.1 degrees C/min) and a relatively fast (3.0 degrees C/min) cooling rate using differential scanning calorimetry (DSC), low resolution NMR, X-ray diffraction (XRD), and polarized light microscopy (PLM). Related forms of the beta' polymorph were detected for all mixtures as well as a beta form for CSC-rich mixtures. A double chain length (DCL) stacking of the non-mixed CCS-CCS and CSC-CSC phases and a triple chain length (TCL) stacking of mixed CCS-CSC structure were detected for the different beta' forms. The kinetic phase diagram demonstrated an apparent eutectic at the 0.5(CSC) composition when cooled at 0.1 degrees C/min and at the 0.25(CSC) composition when cooled at 3.0 degrees C/min. The application of a thermodynamic model based on the Hildebrand equation suggests that compounds CSC and CCS are not fully miscible. In addition, the miscibility changes according to the structure of the growing solid phase which is dependent on CSC molar ratio as well as on the kinetics. It was also shown that the miscibility is concentration dependent and that the solid phase, which is growing at conditions well away from equilibrium, is determined kinetically. The molecular interactions were found to be strong and to favor the formation of CSC-CCS pairs in the liquid state. CSC and CCS were also shown to be immiscible in the solid state. Depressions in solid fat content (SFC) were observed for both rates. Relatively complex networks made of needle-like, spherulitic and granular crystals were observed in the CSC/CCS system. A pure CSC phase was found to be instrumental in promoting a higher SFC, and more stable polymorphic forms. The microstructure was shown to be strongly dependent on the cooling rate and was linked to the different polymorphic forms observed by DSC and XRD. Correlations between SFC and the eutectic behavior have been observed for the 3.0 degrees C/min cooling rate, but not directly in the case of the 0.1 degrees C/min cooling rate, where slower kinetics which favors the metastable to stable phase conversion processes prevented the same shifts in behavior.