Poly (3-phenylthiophene) (P3PhT) films have been electrochemically synthesized by direct oxidation of 3-phenylthiophene in the electrolyte Of pure boron trifluoride diethyl etherate (BFEE). The oxidation potential of the monomer was measured to be 1.29 V (vs. SCE), and about 0.15 V lower than that measured in a neutral medium of acetonitrile. Free-standing P3PhT film with tensile strength of 32-40 MPa has been obtained for the first time. The morphology and the structure of the polymer film have been studied by scanning electron microscopy, infrared and Raman spectroscopies. Raman spectral results demonstrated that the doping level of the P3PhT film increased with film thickness during electrochemical growth process. (C) 2004 Elsevier B.V. All rights reserved.