A kind of azo-containing resin (Azo-R) was synthesized by a simple way through the coupling reaction of 2-nitroN-methyldiphenylamine-4-diazoresin (NDR) with phenol, and a new covalentely attached multilayer film from Azo-R as H-donor and photosensitive diazoresin, diphenylamine-4-diazoresin (DR) as H-acceptor via H-bonding attraction by selfassembly technique has been fabricated. Following the decomposition of diazonium group of DR under exposure to UV light, the H-bonds between the layers of the film convert to covalent bonds and the film becomes very stable toward polar solvents or electrolyte aqueous solutions. Thus the UV-irradiated azo-containing films can be used to measure photocurrent in a conventional three-electrode photoelectrochemical cell using KCl as supporting electrolyte. It was confirmed that the azo-containing multilayer film is responsible for the photocurrent generation.