By Schotten-Bauman’s esterification of amylose with acryloyl chloride, a new ester derivative of starch-acryloyloxyamylose-was prepared, which contains double bonds. The effects of the reagent ratio, KOK concentration, and reaction time on the degree of amylose esterification were examined. The original amylose and acryloyloxyamylose were characterized by FTIR, H-1-NMR, C-13-NMR, GPC, and DSC. Acryloyloxyamylose was polymerized in solution by the free-radical process and by photopolymerization in a solid state to obtain a crosslinked product.