Free-standing poly(para-phenylene) (PPP) films have been electrosynthesized by direct oxidation of benzene on stainless steel electrode in mixed electrolytes of boron trifluoride diethyl etherate (BFEE) and trifluoroacetic acid (TFA). The oxidation potential of the monomer in these media is lower than those in the neutral media. Increasing the content of TFA in the mixed electrolyte can effectively decrease the oxidation potential and increase the coupling rate of the monomer. The films obtained from these media were very shiny and flexible, and could easily be processed into various shapes by conventional mechanical methods. The films had a linear chain structure, and their degree of polymerization could be improved by increasing the TFA content in the mixed electrolyte. Moreover, the films had a fairly good thermal stability.