Polystyrene/high-density polyethylene (PS/HDPE) blends were synthesized by melt blending in a single screw extruder. Co-continuity measurements using solvent extraction and scanning electron (SEM) micrographs showed that co-continuity was obtained around 35% PS. Thermal analyses measurements revealed a reduction in crystallinity of the HDPE phase around the co-continuous composition. Raman analyses across the entire composition range of these blends showed an increase in the normalized integral intensities of the 1128 cm(-1) and 1061 cm(-1) stretching vibrations of the HDPE molecules. The presence of all-trans HDPE chains that are not packed into an orthorhombic structure is used to explain the simultaneous occurrence of reduced crystallinity and increased intensity of all-trans HDPE stretch vibrations.