Poly(p-phenylene) (PPP), an important blue emitter, is difficult to be fabricated in thin film form with a wet process because of its insoluble and infusible characteristics resulting from its rigid backbone structure. Therefore, various indirect and multistep synthetic approaches have been proposed for fabrication of PPP films. In this article, a chemical vapor deposition polymerization process was developed to fabricate successfully PPP films in one-step directly without the often required postreaction thermal treatment. We further demonstrated that the polymer chain conformation of the film can be effectively adjusted through a simple surface treatment of the substrate, and the variations in film morphology induced by the substrate characteristics led to significant changes in the optoelectronic properties of the film.