The present invention discloses a selective preparation method for 5-site and 7-site ester catechin molecules. The selective preparation method comprises: dissolving catechin in acetonitrile, adding benzyl chloroformate and tertiary amine, reacting to obtain 3',4'-dibenzyloxycarbonyl ester catechin, carrying out an acylation reaction of the 3',4'-dibenzyloxycarbonyl ester catechin in the presence of an acylation agent and the tertiary amine to obtain a mixture of 3',4'-dibenzyloxycarbonyl ester-5-ester catechin and 3',4'-dibenzyloxycarbonyl ester-7-ester catechin, and removing the benzyloxycarbonyl from the 3',4'-dibenzyloxycarbonyl ester-5-ester catechin and the 3',4'-dibenzyloxycarbonyl ester-7-ester catechin to obtain the 5-ester catechin and the 7-ester catechin. According to the present invention, the product obtained by adopting the preparation method has characteristics of high purity, good selectivity and good application prospect; and the preparation method has the simple operation, and is suitable for industrial production application.