Fully fluorinated arylenevinylene polymers have been synthesized via a methodology based on the Stille cross-coupling reaction and characterized by FTIR spectroscopy and MALDI-TOF mass spectrometry. Investigation of thin film properties by cyclic voltammetry and ellipsometry shows that complete substitution of hydrogen atoms with fluorine atoms on the conjugated backbone of the poly(arylenevinylene)s results in a strong increase of the band gap. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 285-291, 2010