Abstract: Carboxymethyl-β-cyclodextrins(CM-β-CDs) having different carboxymethylated degrees were synthesized.Their structures and carboxymethylated degrees were characterized by 1H-NMR.A self-assembled multilayer thin-film was fabricated with CM-β-CD as an anion and photosensitive diazoresin(DR) as a polycation based on ionic interaction.The quantity of deposition of self-assembled CM-β-CD/DR films increased with increasing the degree of carboxymethylation of CM-β-CD and the ionic strength of solvent from which CM-β-CD deposited.However,the concentration and pH value of the CMβ-CD aqueous solution had little effect on the self-assembled multilayer films.Under UV irradiation,following the decomposition of diazonium group between the adjacent interfaces of the multilayers,the ionic bonds of the self-assembly film converted to covalent bonds,which improves the stablity of the film effectively.