beta-D-Galactoside branches have been introduced into chitosan and chitin regioselectively through a series of controlled modification reactions based on N-phthaloyl-chitosan. The glycosylation reaction between a chitosan derivative having a reactive group only at C-6 and an orthoester of D-galactose proceeded efficiently to give a protected product with a degree of substitution up to about 0.5. Deprotection gave a branched chitosan, and the subsequent N-acetylation afforded a branched chitin. Unlike chitosan and chitin, the resulting nonnatural branched polysaccharides were characterized by high affinity for solvents and readily soluble in neutral water. Furthermore, branched chitin was easily degraded by lysozyme.