Abstract The lipase catalyzed esterifications of derivatives of propane-1, 2, 3-triol and butane- 1, 2, 4-triol in organic solvents have been studied. The influence of several factors (lipase source, organic solvent, additives and structural variations in the substrates) on the selectivity have been investigated. Good levels of regio-and enantioselectivity have been achieved, providing practical methods for the synthesis of these chiral building blocks.