Donor- or acceptor-substituted polythiophenes have many potential applications in optoelectronics. Fluorinated polythiophenes are particularly attractive because of the presence of fluorine, which can withdraw electrons and also improve polymer chemical stability. Because of the promising future of these polymers, there has been much interest in identifying favorable synthetic routes to new fluorinated monomers and polymers. In this study, the monomer had an electron-withdrawing fluorinated ester and was derived from 3-thiophene carboxylic acid and 2,213,3,4,4, 4-heptafluoro-1-butanol. The synthesis of an n-type fluorinated and terminal-functionalized polythiophene was accomplished with the Ullmann coupling reaction. A polymer soluble in tetrahydrofuran was obtained with a molecular weight of approximately 15,000 g/mol. In solution, it exhibited a band gap of 2.4 eV, and the photoluminescent excitation and emission maxima were 370 nm and 555 nm, respectively. All peaks were bathochromically shifted when they were measured in the solid state. The glass-transition and decomposition (in air) temperatures were 129 and 493 degrees C, respectively. (c) 2005 Wiley Periodicals, Inc.