We report investigations of monolayer films of poly(p-phenylenevinylene) (PPV) adsorbed on both MoS2 and highly oriented pyrolitic graphite (HOPG) surfaces. The monolayer was prepared by deposition of a precursor polymer using the Langmuir-Blodgett technique and subsequent conversion to PPV by thermal treatment in ultrahigh vacuum. Photoelectron spectroscopy and X-ray absorption spectroscopy were used to characterize the conversion and to determine the orientation of the PPV with respect to the substrate sm faces. The appearance of new features in both the X-ray absorption and the valence level photoemission spectra upon conversion can be interpreted in terms of the creation of pi conjugation along the polymer backbone. Additionally, in the angle-resolved photoemission measurements of the fully converted sample on HOPG, a weak dispersion of the pi-derived features is just discernible, The angular dependence of the X-ray absorption spectra shows that the PPV monolayer on MoS2 is highly oriented, with its phenylene and vinylene moieties lying preferentially parallel to the surface.