Poly(4-vinyl phen01) (PVPh) was synthesized from anisaldehyde via Perkin-Doebner and deearboxyl reactions to form 4-methoxy styrene．It was then polymerized by free-radical polymerization following dealkylation to forrtl PVPh．A kind of Stable multilayer utra—thin film was successfully fabrieated via self-assembly technique from PVPh and diazoresin (DR) followed by UV irradiation．The driving foroe of self-assembly was confirmed to be the hydrogen bending attraction from diazonium group(-N2+) of DR and phenolic hydroxy group(一Ph—OH) of PVPh．The film becomes very stable towards polar solvents after UV irradiation and it is believed that the H-bonds between the lalters of the film converts to coValent bonds following the decomposition of —N2+ groups when the multilayer film underwent UV irradiation．