An alternatingly N-sulfonated chitin derivative (2) was synthesized via ring-opening polyaddition of an N-sulfonated chitobiose oxazoline derivative (1) catalyzed by chitinases from Bacillus sp. and Serratia marcescens. The polymerization proceeded homogeneously, providing 2 as a water-soluble polysaccharide in good yields with total control of regioselectivity and stereochemistry. M(n) of 2 reached 1900 and 4180 by use of chitinases from Bacillus sp. and Serratia marcescens, which correspond to 8-10 (n = 4-5) and 18-20 (n = 9-10) saccharide units, respectively. These results indicate that M(n) of 2 is controllable by selecting chitinases from different origins. It is considered that the C-2 position of the nonreducing unit in the oxazoline-type monomer is not deeply involved in the catalysis of chitinase.