Cellulose-chitin hybrid-type branched polysaccharides, beta-1,4-d-glucans having amino sugar branches at the C-6 position, have been synthesized through a series of site-specific modification reactions. Cellulose was first transformed to two kinds of acceptors having a reactive group only at C-6. Glycosylation reactions of these acceptors with an oxazoline donor derived from d-glucosamine resulted in the introduction of amino sugar branches into cellulose. An acceptor carrying the O-trimethylsilyl group at C-6 was particularly suitable for glycosylation in solution to form branched celluloses with various degrees of substitution up to about 0.5 per pyranose unit in a controlled manner. Deprotection of the product afforded the cellulose having N-acetyl-d-glucosamine or d-glucosamine branches depending on the reaction conditions. The deprotected nonnatural branched polysaccharides were readily soluble in neutral water as well as common organic solvents and would be promising as a new type of water-soluble amino polysaccharides.