The invention discloses a preparation method and an application of a corn amylose supported catalyst. The preparation method comprises steps as follows: firstly, corn amylose is puffed for increasing the specific surface area and pore volume; then, the puffed corn amylose and 3-aminopropyltriethoxysilane are subjected to a reaction, and ammonified corn starch is obtained; finally, the ammonified corn starch and an acetylacetone metal complex are subjected to a Schiff base reaction, and the corn starch immobilized catalyst is obtained through condensation. The corn amylose supported catalyst can be applied to catalysis of vegetable oil for an epoxidation reaction, and epoxidized plant oil is obtained. The solid catalyst synthesized with the preparation method overcomes the defect of a homogeneous catalyst, and has the advantages of being easy to prepare, green, environment-friendly, high in catalytic activity, reusable and low in cost, and is a good solid catalyst for an olefin carboamidation reaction, oxicracking of an aryl epoxy compound, oxidation of thioether, an epoxidation reaction of olefin and the like.