The enzymatic transesterification of fatty acid methyl esters from vegetable oil and polyglycerol has been successfully performed in the presence of Lipozyme without any solvent. The optimal conditions to obtain a mixture with lipophilic tensioactive properties were found to be a molar ratio of fatty acid methyl esters and polyglycerol of 1.33:1 at 60 degrees C. Evaporation of the methanol produced in this reaction increased the yield of the reaction. Moreover, for this reaction, adsorption of the polyol on silica gel prior to the transesterification allowed the completion of the reaction and improved the kinetic properties. Hydrophile-lipophile balance and surface activity of the polyglycerol esters were measured to determine the emulsifying properties of these molecules.