The optimized synthetic procedures are given that lead to stretched poly(p-phenylenevinylene) (PPV) films of high molecular alignment and chemical homogeneity. Films of sulfonium precursor, pristine PPV, and FeCl3-doped PPV are fully characterized spectroscopically as well as by electron microscopic and electron diffraction techniques. In particular, the paracrystalline structure of PPV is examined and the fluctuation values of the average cell edge vectors are measured; the values Delta(11)(3) = Delta(22)(3) > 0.27 Angstrom and Delta(33)(3) < 0.12 Angstrom were obtained. Furthermore, the molecular orientation in films of the precursor, the stretched pristine, and stretched, FeCl3-doped phases is investigated. An angular distribution function about the stretching direction is measured and tested against the pseudo-affine (Kratky) deformation model.