Phase-equilibrium diagrams of biodiesel synthesis substrate (oil/alcohol/alkyl esters) and product (alkyl esters/glycerol/alcohol) mixtures containing methanol, ethanol and propanol, respectively, were used for the identification of those composition ratios leading to mixture homogeneity. Based on the diagrams, complete conversion of the substrate oil contained in a sunflower oil/ ethanol/ethyl ester mixture at a weight ratio of 7.6:11.4:81.0 resulted in the generation of an amount of glycerol capable of remaining in solution in the product mixture. In contrast, complete conversion using a mixture of a lower alcohol and ethyl ester content (19.0:6.0:75.0) leads to the separation of phases. A continuous reactor charged with Lypozyme TL-IM and fed with the former mixture showed constant conversion and productivity with time, whereas process efficiency was found to decrease drastically when the latter mixture was fed. When a sunflower oil/isopropanol/isopropyl ester mixture at a weight ratio of 35:35:30 was fed in the reactor charged with Novozym 435, the output glycerol concentration was equivalent to that theoretically expected. In contrast, feeding a sunflower oil/ethanol/ethyl ester mixture of equal proportions as above, the glycerol concentration was lower than expected, suggesting the occurrence of glycerol adsorption on the enzyme support.