In this study, the synthesis of a novel cationic coumarin-containing polymer (C-CPA) was presented. C-CPA was examined optically using photoluminescence (PL) spectroscopy. The optical data suggested that they were promising blue-emitting materials mainly due to the coumarin chromophore on the side chain. Moreover, the synthesized cationic polymer was suitable for layer-by-layer electrostatic self-assembly thin film deposition from dilute polymer solution and multilayers were fully characterized by UV-vis spectroscopy, PL spectroscopy and atomic force microscope. (c) 2008 Wiley Periodicals, Inc.