Poly(p-phenylene) (PPP) films have been electrochemically deposited on mirrorlike stainless steel (SS) electrode surfaces by direct oxidation of benzene in boron trifluoride diethyl etherate (BFEE) solutions at a constant applied potential of 1.7 V (versus Ag/AgCl). The chain conformations of as-grown PPP films have been studied by Raman spectroscopy. The results demonstrated that high synthesis temperature favors the formation of planar PPP, and the conformation of planar PPP can be changed into torsional PPP by cooling treatment.