Chemical interesterification reaction conditions that provide regioselectivity regarding fatty acid positions in triacylglycerol have been investigated. Sodium methoxide‐catalyzed ester interchange between soybean oil and methyl stearate was performed in hexane at low reaction temperature,i.e., 30 to 60°C. The results showed regioselectivity was obtained at 30°C. The ester interchange at 1,3‐carbons progressed 1.7 times faster than at 2‐carbon of the glycerol moiety of triacylglycerol at 24 h. Preheating of the mixture of reactant and catalyst at 60°C for 15 min promoted catalyst activation to accelerate the interesterification while maintaining regioselectivity. This method is believed to be feasible for modification of edible fats and oils.