Chitosan–N-poly(ethylene glycol) brush copolymers with different degree of substitution (DS) were synthesized via reductive amination of chitosan by methoxy poly(ethylene glycol) (MPEG) aldehyde. Chitosan–N-MPEG copolymers were high-molecular-weight products with desirable DS; solubility and solution viscosity of those copolymers depended on the method of the synthesis of MPEG aldehyde and on DS. Synthesis of MPEG aldehyde by the use of TEMPO radical/BAIB was not suitable because of partial oxidation of methoxy groups of MPEG resulting in bifunctional PEG derivatives leading to cross-linking. Adsorption studies of chitosanÅ|N-MPEG graft copolymers on silica surface show that these polymers adsorb in highly hydrated layers