The process relates to the very selective enzymatic production of monosaccharides and polyols which are mono and/or bisubstituted with fatty acids. The process is based on the simple mixing of polyol or monosaccharide with the fatty acid, the addition of solvent, and the use of lipases in order to regioselectively obtain them without catalysts or toxic agents. The process requires continuous removal of water produced during the process. The invention applies to the sectors such as food, pharmaceutics, cosmetics and chemistry. The products obtained are excellent non ionic surfactant agents, which are biocompatible and biodegradable and are used as additives due to their emulgent, unctuous, thickening and hydrating characteristic.