An air and moisture stable ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)) was utilized as an electrolyte for the direct anodic oxidation electropolymerization of fluorene. The corresponding electroactive polyfluorene films showed good redox activity and structural stability. H-1 NMR and FTIR spectra together with density functional theory calculations indicated that the polymerization of fluorene Occurred at the C-2 and C-7 positions. Scanning electron microscopy results demonstrated that smooth and compact polyfluorene films were obtained, due to the use of bmimPF(6) as both the growth medium and the electrolyte. Doped polyfluorene films were examined to oxidize formic acid in 0.5 mol/L sulfuric acid by cyclic voltammetry and demonstrated stable electrocatalytic activity, showing their potential use in fuel oxidation. (C) 2009 Elsevier B.V. All rights reserved.