The effect of molecular structure of styrene–butadiene block (SB) copolymers on the morphology, tensile properties, impact strength, and microhardness of polypropylene/polystyrene (PP/PS) (80/20) blends was studied. The addition of SB copolymers substantially reduces the size of dispersed PS particles formed at mixing. The distribution of SB copolymers between the interface and bulk phases is controlled by the length of styrene blocks in SB, but a decrease in the size of PS particles at mixing correlates with total molecular weight of SB copolymers. For a substantial part of compatibilized blends, PS particles aggregate rapidly during compression molding and form honeycomb‐like particles split by SB partitions, which persist at further annealing. Aggregation of PS particles continues slowly at further annealing. Blends containing PS particles with well‐developed honeycomb structure show lower yield stress, higher plasticity, and lower tensile impact strength than the blends having PS particles with simple or undeveloped honeycomb structure. Microhardness of PP/PS blends is additive and of PP/PS/SB blends is lower than the additive due to the effect of SB copolymers on crystalline structure of PP matrix. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers