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An approach to the preparation of pullulan-graft-poly(2-methyl-2-oxazoline)s based on Cu-catalyzed azide–alkyne cycloaddition with polyoxazoline-azide was applied. All of the obtained polymers were characterized through classical molecular hydrodynamic methods and NMR. The formation of graft copolymers was accomplished by oxidative degradation of pullulan chains. Nevertheless, graft copolymers were obtained as uniform products with varied side chain lengths and degrees of substitution.