Abstract: Crosslinked microporous starch was prepared with cassava starch as raw materials, phosphorus oxychloride as crosslinking agent, glucoamylase and alpha amylase as composite enzyme.The results showed that the dosages of starch content, crosslinking agent and composite enzyme, pH, reaction temperature and reaction time remarkable influenced the performance of crosslinked microporous starch.The optimum technological conditions were starch content 30%, crosslinking agent for 80μL, pH4.5, compound amylase amount of 2.0%, enzymatic hydrolysis temperature at 50℃ and enzymatic hydrolysis time of 12h.The structure and morphology of the crosslinked microporous starch were characterized by SEM, XRD and TGA.