Sorbitol fatty esters have been prepared through a two-step catalytic process which involves the protection of the polyalcohol by ketalization followed by esterification with the fatty acid. Inorganic molecular sieves with different pore topologies as well as heteropolyacids (HPA) were used as acid catalysts to perform both the ketalization and the esterification step. These catalysts are found to hydrolyze the ketal function and promote the esterification between the free hydroxy groups and oleic acid in a cascade process. The results show a positive shape-selectivity effect when the process is carried out using tridirectional, and especially monodirectional (mordenite), zeolites, such that the ratio of mono- to higher esters and the hydroxy number of the final product are increased as compared to those obtained for the homogeneous-catalyzed process.