Abstract: Supermolecular complex PCAMSTIL containing photosensitive unit (cinnamate) and fluorescent unit (stilbene) was prepared by ionic selfassembly (ISA) method. The structure of the complex was characterized by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR). The thermal stability and optical property of the complex was studied by thermogravimetric analysis (TGA), ultraviolet visible spectroscopy(UV-Vis) and fluorescence spectium(FL). Irradiated by 266 nm polarized laser caused cinnamate group to undergo axisseletive ［2+2］ photocycloaddition, resulting in an alignment of cinnamate group perpendicular to the polarization direction leading to dichroism value of 0.103. The laserinduced orientation of cinnamate group had a cooperative effect on alignment of the stilbenebased fluorescent unit. So the fluorescence emitted by the oriented film was polarized and the ratio of anisotropic fluorescence was 1.73.