omega-Pyrenyl-functionalized poly(1,3-cyclohexadiene) (PCHD) was successfully synthesized by the postpolymerization reaction of poly(I,3-cyclohexadienyl)-lithium (PCHDLi) with 1-chloromethylpyrelle (CIMe-PY). This postpolymerization reaction consisted of two competitive reactions: the addition reaction of the pyrenyl group, and a hydrogen abstraction reaction (lithiation) as a side reaction. The degree of nucleophilicity of PCHDLi was a very important factor for suppression of the Side reaction, and the PCHDLi/amine system, which has high nucleophilicity, produced high omega-pyrenyl-functionalized for PCHD. The UV/vis and fluorescence spectra for omega-Pyrenyl-functionalized PCHD were bathochromically shifted, relative to that of pyrene. (c) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 2006-2010, 2009