Low calorie triacylglycerols (TAG) presenting medium-chain fatty acids (M) at positions sn-1,3 and long-chain fatty acids (L) at position sn-2 are known as MLM. This study aims at the production of MLM by acidolysis of grapeseed oil with medium-chain caprylic (C8:0) or capric (C10:0) acids. Grapeseed oil is used as source of long-chain polyunsaturated fatty acids (FAs), especially linoleic acid, at sn-2 position in TAG. Reactions are performed in batch, in solvent-free systems, during 48 h. Novel non-commercial sn-1,3 regioselective lipases are used as alternative to high-cost commercial biocatalysts, namely, the heterologous lipase from Rhizopus oryzae (rROL) immobilized in Amberlite TM IRA 96 and Carica papaya lipase (CPL)self-immobilized in papaya latex. The highest productions of new TAG are achieved at 40 C, molar ratio TAG:M of 1:2, after 48 h, with both biocatalysts, with yields varying between 38 and 69%. rROL immobilized in Amberlite IRA 96 shows a preference toward caprylic acid while CPL shows no preference toward caprylic or capric acid. First-order deactivation kinetics is observed for both biocatalysts. Halflives at 40 C are 166 and 118 h for rROL and 96 and 81 h for CPL, in the acidolysis of grapeseed oil with C8:0 or C10:0, respectively. Practical Applications: Grapeseeds of Vitis vinifera L. are a by-product of the wine industry. Using grapeseed oil to produce added-value functional oils rich in linoleic acid (essential fatty acid) may be a way of improving the revenues of the enological and oil sectors. Both lipases, and mainly Carica papaya lipase self-immobilized in papaya latex, due to its low-cost production and easy preparation, are promising non-commercial biocatalysts for the synthesis of MLM in solvent-free media. The use of a solvent-free system, in addition of being a green option, is also preferred for economic reasons, avoiding the costs with solvent and solvent recovery.