Two methods have been developed for the preparation of biaxially oriented poly(phenylene vinylene) from its poly(sulfonium salt) precursor. A two-stage stretching process permits non-equibiaxial stretching over a wide range of deformation ratios and a bubble expansion technique allows equibiaxial planar extension. The resulting films were examined using X-ray diffraction prior to chemical doping with SbF5 vapor. Biaxial orientation was shown to exert considerable influence over the attainable electrical conductivity.