Orientation of azo chromophores in electrostatic self-assembled multilayer films of four side-chain azo polyelectrolytes that contain azobenzene derivatives with different p-substituents was investigated by using polarized UV-Vis absorption spectroscopy．Influences of substituents on the orientation of the azo chmmophoms were discussed in detail The structural characteristics of these self-assembled films were further investigated．It was found that the homogeneous oriention tendency of azobenzene was a common phenomenon in the self-assembled films fabriemed by electrostatic layer-by-layer dipping process of the side-chain azo polyeleetrolytes and poly (diallyldimethyl armnonium chloride)：suhstituents that link to azobenzene have influences on the orientmion of azobenzene in self-assembled films

which could be attributed to charge interaction and dipolar interaction between the ehromophores and the polycation substrates．For those self-assembled muhilayers with H-aggregation．the effect of substituents on the orientation of azobenzene was also influenced by the H-aggregation．The results indicate that the orientation of azobenzene in self-assembled films can be effectively adjusted by selecting polyelectmlytes containing azobenzenes with different p-substituents．