Using the self assembly technique, a stable multilayer films was successfully fabricated from diazoresin (DR) and poly(styrene-co-(N-(p-hydroxyphenyl)maleimide)) (P(S-co-HPMI)) followed by UV irradiation. The driving force of the self-assembly was confirmed to be H-bonding attraction between the diazonium group (-N-2(+)) Of DR and the phenolic hydroxy group (-Ph-OH) of P(S-co-HPMI). A linkage conversion from H-bond to covalent bond takes place after decomposition of the -N-2(+) group using UV irradiation. As a result, the stability of the film towards polar solvents increases dramatically.