Photo-induced molecular alignment behavior of spin-coated poly(4,4'-azo benzene pyromellitamic acid) (PAA(azo)) film was investigated by Fourier transform infrared spectroscopy measurement, atomic force microscope and transmission electron microscope observation. As-spun PAA(azo) flm was found to be smooth and uniform with an amorphous structure. Upon irradiation of linearly polarized ultraviolet light, the molecular ordering and crystallization were induced, and the film surface was roughened slightly. The PAA (azo) film converted to poly(4,4'-azobenzene pyromellitimide) (PI(azo)) film with higher ordering and crystallinity by subsequent thermal treatment. The PI(azo) film was useful as an active layer to introduce the molecular alignment of copper phthalocyanine (CuPc). (C) 2009 Elsevier B.V. All rights reserved.