The invention discloses a preparation method and application of a cross-linking type polymerization catalyst. The preparation method is characterized by including performing a synthesis reaction to form an intermediate compound of which molecule contains vinyl benzene by using cinchona alkaloid and derivative of vinyl benzene, and performing a polymerization reaction of the intermediate compound and the cross-linking agent divinyl benzene to form a polymer catalyst in the presence of an initiator. The catalyst is used for an asymmetric alpha-chlorination catalytic reaction of beta-ketonic ester and chlorinated reagent, has high catalytic activity, is easy to separate, and can be recycled. Compared with the prior art, the preparation method has simple preparation, easy operation, easy post-treatment, high raw material utilization ratio, optimized reaction condition and reduced reaction requirement, especially is used for the compound obtained by constructing a chiral center on the different carbon of beta-ketonic ester, and has an important practical significance of researching medicinal chemistry and medical intermediate compound.