The fractionation of oils has received considerable research attention, aiming at the modification of the properties of oils. The thermal and crystallization properties of palm kernel oil (PKO) and its olein/stearin (PKOL/PKST) were systematically investigated using differential scanning calorimetry (DSC). Based on the isothermal DSC results, crystallization temperature exerted critical effect on co-crystallization of PKOL and PKST. Moreover, it is reported that PKOL could be further separated by controlling the crystallization temperature, while PKST is hard to be further separated. The PKOL/PKST mixtures with different compositions were prepared and subjected to dynamic DSC analysis. The results illustrated that PKO meets the phase equilibrium of quasi-solid solutions.