The effect of cooling rate on the crystallization behavior of mixes of high-melting milk fat fraction (HMF) and sunflower oil (SFO) was studied by following nucleation with laser-polarized turbidimetry. The initial crystals were photographed, and their thermal and polymorphic behaviors, as well as chemical composition, were investigated by calorimetry, X-ray diffraction, and capillary gas chromatography. Activation energies of nucleation were calculated using the Fisher−Turnbull equation. Despite small differences in Mettler dropping points for different ratios of SFO to HMF, induction times were significantly different between samples and were shorter at a slow cooling rate for the same supercooling. Rapidly cooled samples required more time at crystallization temperature to crystallize than slowly cooled samples because molecular organization prior to nuclei formation took place under different conditions. Regardless of cooling rate or composition, all crystals were in the β‘ polymorph. However, morphology, thermal behavior, and chemical composition showed differences with cooling rate. Activation free energies of nucleation were of the same order of magnitude as those published for hydrogenated SFO.