Palmitoyl-oleoyl-oleoyl (POO) and palmitoyl-oleoyl-palmitoyl triacylglycerol rich fraction (PSL) was obtained from the acetone fractionation of palm stearin. The fatty acid composition (total and positional), triacylglycerol species, and solid fat index (SFI) were compared among the blends of natural vegetable fats (sal fat, illipe fat, kokum fat, shea stearin fat, and shea butter) and PSL with different ratios (50:50, 60:40, 65:35, 70:30). In total fatty acid composition of PSL, palmitic, oleic, and linoleic acids were the major fatty acids, whereas in natural vegetable fats stearic and palmitic acids were the major fatty acids. Moreover, oleic acid was a major fatty acid at sn-2 position in sal fat, illipe fat, and kokum fat. The TAG species was analyzed by reversed-phase HPLC, from which the PN value ranged from 46 to 54. When natural vegetable fats and PSL were blended with different ratios, decreasing the amount of PSL resulted in increasing SFI in most cases. Among blends, the SFI of sal fat and PSL were most similar to commercial cocoa butter equivalent (CBE).