Highly anomer-selective-6(6')-acylation reactions from anomeric mixtures of several mono- and disaccharides with divinyl dicarboxylates ranging from 4 to 10 carbon atoms were catalyzed by an alkaline protease from Bacillus subtilis in pyridine. A series of new pure alpha-anomeric polymerisable vinyl sugar esters of dibasic acids were synthesized in good selectivity and yields.