Poly(4-diazosulfonate styrene-co-4-vinylpyridine) (P(DSS-co-VP))

containing both H-acceptor moieties of pyridine and photosensitive diazosulfonate groups

was synthesized and has been used for self-assembly as a new component．The layer-by-layer deposition between P(DSS-co-VP)and m-methyl phenol formaldehyde resin (MPR) on a substrate via H-bonding interaction was investigated．After UV irradiation the stability of the multiplayer ultra thin film toward polar solvents is improved dramatically. The improvement of the solvent stability of the film should be attributed to the bond conversion between the layers of the film from H-bond to covalent bond under UV irradiation.