The effect of thermal treatment on the mechanical performance of biaxially oriented poly(p-phenylene sulfide) by cold roll milling was studied. It was found that the ductility of the cross-rolled material could be further enhanced by annealing at temperatures above Tg and the yield strength could be enhanced by annealing at temperatures below Tg with a partial loss in ductility. Two-dimensional wide-angle X-ray diffraction patterns suggested a reduced crystallinity in the rolled material and showed that the crystal structure of the unrolled material could be partially recovered by annealing above Tg; however, scattering patterns adjacent to the crystalline reflections persisted with heat treatment. Modulated differential scanning calorimetry (MDSC) and broadband dielectric spectroscopy indicated that cross-rolling altered the kinetics of the cold-crystallization process. MDSC and dynamic mechanical analysis measured a reduction in Tg suggesting enhanced molecular mobility as an outcome of cross-rolling. After annealing at temperatures well beyond Tg, a large reduction in elongation to failure was observed, and the material could not cold draw. These results suggest that a two-stage process involving plastic deformation by roll milling followed by annealing treatment may be used to commercially produce high toughness and yield strength sheet products from commercially available resins.