The crystalline structure and morphology have been investigated for powder processed poly(phenylene sulfide) blended with high-density polyethylene and poly(tetrafluoroethylene). The crystallinity in the former case showed large deviations from those estimated from rule of mixtures, while in the latter blends it closely followed the values predicted from the linear relation for homogeneous mixtures. Pronounced changes in some reflections were found in the X-ray pattern on thermal curing of the samples. These results have been explained on the basis of compaction behavior of the powder blends together with the orientations induced during the processing steps.