In this paper, a new layer-by-layer (LBL) ultrathin film with photosensitive cinnamoyl chromophores was prepared. It could induce uniforrn alignment of liquid crystals (LC) after irradiated by linearly polarized ultraviolet (LPUV) light. First, a photosensitive polycation containing cinnamoyl side groups was synthesized. Then a layer-by-layer ultrathin film was prepared in an aqueous solution of the polycations and poly (sodium 4-styrenesulphonate). The spectra of UV-vis absorption and ellipsometric measurement showed that the LBL film was uniform and suitable for the photoalignment of LC. When the film was irradiated by LPUV light, the cinnamoyl units in the film underwent [2 + 2] cycloaddition along the electric vector direction of the LPUV light. The polarized UV-vis spectra also proved that the film was anisotropic, and then the film could induce the homogeneous alignment of nematic LC. With the number of bilayers increasing, the alignment effect of multilayer film became better, and the contrast ratio became higher. (c) 2006 Elsevier B.V. All rights reserved.