An efficient procedure for the lipase-catalyzed esterification of starch has been established in a solvent-free medium. Corn starch was used as the acyl acceptor and oleic acid was used as the acyl donor. In order to improve the reactivity of native starch (NS), it was pretreated with NaOH/Urea hybrid solution at cool temperature below -10 °C. The esterification of starchwas carried out at different initial aw, temperatures for different times. The amount of lipase and the ratio of starch to oleic acid also had been studied. The maximum degree of substitution of starch oleate 0.229 was obtained by the presented method. The NS, pretreatment starch (PS) and starch oleate (SO) were analyzed bymeans of SEMtechniques, FT-IR and 1HNMR.