The electronic structure of a conjugated polymer of current interest in organic LED’s, poly(p-phenylenevinylene), or PPV, has been studied by ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy. The focus of this work is on the nature of the pi-electronic band structure nearest the Fermi level and the physical influence of finite torsion angles, the geometry of the polymer backbone, on the electronic properties of the system. Details of the ct-electronic bands, as reflected in the associated density-of-states, are observed clearly in the spectra, from which some underlying geometrical details of the polymer system can be deduced. The experimental spectra have been analyzed theoretically using band structure calculations based upon the valence effective Hamiltonian (VEH) model. In addition, in order to control the band structure, three ring-substituted derivatives of PPV, each of which induces a different bonding geometry in the backbone, have been studied. The changes in the experimental results can be explained on the basis of both physical and chemical interactions of the substituents with the backbone, which lead to geometrical changes along the backbone, which influence the ct-bandwidths and contribute to differences in both the optical absorption threshold and the binding energy of the valence band edge.