Oriented films of poly(p-phenylene) (PPP) were prepared by two methods. One was the friction-deposition technique, in which sliding the solid PPP on the substrate at a controlled temperature afforded a highly oriented film on the surface. In another method, when the friction-deposited film was immersed into the reaction mixture, benzene was polymerized into the oriented PPP film on the friction-deposited substrate. Both oriented films of PPP were characterized by electron microscope and polarized spectroscopic methods.