The liquid-phase MgO-promoted glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), to give acylglycerol products was studied both, experimentally and by density functional theory (DFT). Catalytic results showed that strongly basic low coordination O2- surface sites participate in kinetically relevant steps of the glycerolysis reaction. Changes in the selectivity toward the different mono- and diglyceride isomers were investigated by varying the reaction conditions. The main product was always alpha-glyceryl monooleate (alpha-MG), a monoglyceride with the ester fragment at one of the terminal positions of the glycerol molecule; the beta-MG isomer, with the ester substituted at position 2 was obtained in much lower amounts. The molecular modeling of glycerol (Gly) and FAME adsorptions as well as of the glycerolysis reaction was carried out using periodic DFT calculations and a model of stepped MgO surface. Results indicated that FAME was more weakly adsorbed than Gly; the latter adsorbs on a coordinatively unsaturated surface O2- site with O-H bond breaking at position 2 of the Gly molecule, giving therefore a surface beta-glyceroxide species. Calculations explained the apparent contradiction-between-the preferential formation-of the alpha-MG isomer and the energetically favored dissociation of the secondary OH group of Gly that leads to the beta-glyceroxide species. They predict that the beta-glyceroxide species participates in the pathways conducting to both, alpha- and beta-MG isomers. Synthesis of alpha-MG occurs by C-O coupling of beta-glyceroxide with FAME at one of the two primary OH groups of the beta-glyceroxide species. Two transition states (TS) and a tetrahedral intermediate (TI) are involved in both, alpha-MG and beta-MG isomer formation. However, the pathway toward beta-MG is limited by the large sterical effects associated to the TI formation. Contrarily, the TI leading to alpha-MG is relatively easy to form. (C) 2015 Elsevier Inc. All rights reserved.