Novel chitosan-N-inulin graft copolymers with different degree of substitution (DS) of chitosan were synthesized via water-soluble 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide mediated reaction. Chemical structure and composition of the chitosan derivatives was confirmed by chemical analysis, FT-IR, XPS, 1 H and 13 C NMR spectroscopy, and potentiometry. Chitosan–inulin copolymers were high-molecular-weight hydrophilic products soluble in water in a wide pH range forming extraordinary viscous solutions. Intrinsic viscosity of N-modified chitosans was sharply suppressed by added electrolyte and had tendency to decrease at higher DS of chitosan. pK α values of the chitosan–inulin copolymers determined from potentiometric titration data using Henderson–Hasselbalch equation were in the range 6–7 slightly increasing at higher DS. Novel water-soluble chitosan copolymers retained cationic properties of chitosan and could be used as surface conditioners.