In this study, polystyrene-hydrogenated polybutadiene-polystyrene (SEBS) triblock copolymer was used as a compatibilizer for the blends of polystyrene (PS) and high-density polyethylene (HDPE). The morphology and static mechanical and impact properties of the blends were investigated by means of scanning electron microscopy, uniaxial tension, and instrumented falling-weight impact measurements. Tensile tests showed that the yield strength of the PS/HDPE/SEBS blends decreases considerably with increasing HDPE content. However, the elongation at break of the blends tended to increase significantly with increasing HDPE content. The excellent tensile ductility of the HDPE-rich blends resulted from shield yielding of the matrix. Charpy impact measurements indicated that the impact strength of the blends increases slowly with HDPE content up to 50 wt %; thereafter, it increases sharply with increasing HDPE content. The impact energy of the HDPE-rich blends exceeded that of pure HDPE, implying that the HDPE polymer can be further toughened by the incorporation of brittle PS minor phase in the presence of SEES compatibilizer. The correlation between the impact property and morphology of the blends is discussed.