High quality polymer films can be easily produced by low-potential anodic oxidation of fluorene and its alkyl-polymer precursor through 9,9 position (9,9-dibromohexylfluorene, 9-(6-bromohexyl)fluorene, poly(fluorene-9,9-diyl-alt-alkan-1,6-diyl); Scheme 1) in boron trifluoride diethyl etherate (BFEE) or mixed electrolytes of BFEE+CHCl 3 . As-formed polymer films showed good redox behavior and were characterized by UV–vis, infrared, fluorescence spectroscopy and thermal analysis. Fluorescence spectral studies both in solution and in solid-state revealed that as-formed polymer films were good blue-green light emitters with strong emissions at about 420 and 560nm. The substitutions of alkyl group and alkyl-polymer fluorene precursors were helpful for the red shift of emission wavelength of as-formed polyfluorenes.