Photosensitive polymer materials with photo-cross-linkable side chain group were prepared based on ionic self-assembly technology. The complex materials were constructed by the coupling of polyelectrolyte and cinnamate units with different spacer length (6 or 12 methylene units designated PCAM6 and PCAM12, respectively). Photochemical properties including photo-cross-linking and photoinduced alignment of such a complex materials with transparency in a visible region were investigated by irradiating with a polarized laser. Furthermore, a homogeneous and stable liquid crystals' alignment was achieved on the resultant anisotropic orientation film. This facile method to construct photosensitive polymers would be very attractive due to its practical applicability in versatile optical elements with birefringent characteristics. (c) 2009 Elsevier Ltd. All rights reserved.