Electrochemical polymerization of furan was achieved in acetonitrile/boron trifluoride/ethyl ether (CH3 CN/BF3/EE) mixture in the presence of tetrabutylammonium tetrafluoroborate via constant potential electrolysis at 1.4 V versus Ag/AgCl. Electrochemical behavior of furan was investigated in the same solvent mixture of varying ratios, utilizing cyclic voltammetry. Free-standing polyfuran (PFu) films were obtained in CH3CN/BF3/EE mixture (2/4/4; v/v/v) and characterized using FTIR spectroscopic technique. Spectroelectrochemical behavior of the PFu film was investigated by recording the electronic absorption spectra, in sitn, in monomer-free solution. It is observed that PFu film can be reversibly cycled between -0.1 V (gray) and + 0.6 V versus Ag-wire (gray color); however, this behavior diminishes in the presence of water. Electrochromic device application of PFu film with poly(ethylene dioxythiophene) was also studied. (c) 2006 Wiley Periodicals, Inc.