High-quality freestanding and conducting poly[3-(6-bromohexyl)thiophene] (PBHT) films with electrical conductivity of 20 S/cm were synthesized electrochemically by direct anodic oxidation of 3-(6-bromohexyl)thiophene (BHT) in boron trifluoride diethyl etherate (BFEE). The oxidation potential of BHT in pure BFEE was measured to be only 1.2 V versus saturated calomel electrode, SCE much lower than that determined in acetonitrile (ACN) (1.8 V vs SCE). The polymer films obtained from this media were very shiny and flexible and can be easily cut into various shapes. The structure and morphology of the polymer films were investigated by UV-vis, infrared, H-1-NMR spectroscopy, thermal analysis, and scanning electron microscopy (SEM). All these results indicated that the terminal bromide did not have negative effect on the electrochemical polymerization of BHT. (C) 2008 Wiley Periodicals, Inc.