The present study aimed to develop a heterogeneous catalysis process for diacylglycerols (DAG) production through low‐temperature chemical glycerolysis. Of the heterogeneous catalysts evaluated, MgO‐supported KOH (KOH–MgO) was found effective for the low‐temperature chemical glycerolysis, and the KOH–MgO was characterized by FT‐IR and powder XRD. Reaction temperature was of paramount importance and 80°C was found necessary to enhance the present reaction. Molar ratio of oil to glycerol at stoichiometric ratio (2:1) gave more DAG formation. 41.8 ± 0.8 wt% of DAG was obtained under these conditions: KOH–MgO concentration 4.5 wt% based on oil, acetone dosage 3:1 (acetone to oil in weight ratio), molar ratio of oil to glycerol 2:1, reaction temperature 80°C and time 12 h.Practical applications: Heterogeneous catalysis has been recognized as green process, it is advantageous over the homogeneous catalysis in terms of separation and reusability of catalysts. The MgO‐supported KOH catalyst described in this study can effectively catalyze the low‐temperature chemical glycerolysis, it could be considered for practical applications.