High-quality poly(9,9-dichlorofluorene) (PDCF), a new part soluble polyfluorene derivative, was easily synthesized electrochemically by direct anodic oxidation of 9,9-dichlorofluorene (DCF) in boron trifluoride diethyl etherate (BFEE) containing 15% (by volume) trifluoroacetic acid (TFA). It was hard for DCF to deposit on the electrode in neutral solvents such as CH3CN system. This methodology may help promotion of researches to reveal unknown properties and applications of polyfluorene materials. PDCF films with conductivity of 3.3 x 10(-2) S cm(-1) obtained from this media show good redox activity and thermal stability. The structure and morphology of the polymer were studied by UV-vis, FTIR, H-1 NMR spectra, and scanning electron microscopy, respectively. The results of quantum chemistry calculations and the spectroscopies of dedoped PDCF indicate that the polymerization of DCF mainly occurs via C-(2) and C-(7) position. Fluorescent spectral studies indicate that PDCF film with high fluorescence quantum yields and photochemical stability is a novel green light emitter. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1791-1799, 2010