A series of N-alkyl/aryl carbazole 3,6-substituted arylene trifluorovinyl ether (TFVE) monomers were synthesized in high purity and yield from a concise four-step synthesis using carbazole as a starting material. Condensate-free, step-growth chain extension of the monomers afforded perfluorocyclobutyl (PFCB) arylene ether homo- and copolymers as solution processable, optically transparent blue-light emissive materials. Arylene TFVE monomers and conversion to PFCB arylene ether polymers were structurally elucidated and purity confirmed by high resolution mass spectroscopy, NMR (H-1, C-13, and F-19) spectroscopy, gel permeation chromatography, and attenuated total reflectance Fourier transform infrared analysis. Thermal analysis by differential scanning calorimetry and thermogravimetric analysis revealed glass transition temperatures >150 degrees C and onset of decomposition in nitrogen >410 degrees C with 40 wt % char yield up to 900 degrees C. Optical and electrochemical studies included solution (tetrahydrofuran) and solid state (spin cast thin film) UV-vis/fluorescence spectroscopy and cyclic voltammetry which showed structure dependence of these blue emissive systems on the nature of the N-alkyl/aryl carbazole substitution in either homo- or copolymer configurations. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 552-560