High-quality poly(2-phenylindole) (PPI) films were synthesized electrochemically by direct anodic oxidation of 2-phenylindole (PI) in boron trifluoride diethyl etherate (BFE). The onset oxidation potential of PI in this medium was measured to be only 0.83 V versus a saturated calomel electrode (SCE), which was much lower than that determined in acetonitrile (ACN) containing 0.1 mol L-1 tetrabutylammonium tetrafluoroborate (1.05 V vs. SCE). PPI films, obtained from BFEE showed good electrochemical behavior and thermal stability with an electrical conductivity of 10(-2) S cm(-1). Structural studies showed that the polymerization of PI mainly occurred at the 3,6-positions. As-formed PPI films could be partly dissolved in dimethyl sulfoxide. Fluorescence spectral studies indicated that PPT was a blue-green light emitter. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 96-103, 2009