The. effect of molecular structure of styrene-butadiene (SB) block copolymers on their interfacial activity in low-density polyethylene/polystyrene (LDPE/PS) (4/1) blends was studied. It was found that addition of some SB copolymers, which are localized in brittle PS particles, leads to a decrease in the blend impact strength in spite of the fact that these SB improve the toughness of both the blend components. Comparison with our previous results showed that the distribution of SB copolymers between the interface and bulk phases and their supermolecular structure in LDPE/PS (4/1) blends strongly differs from those in LDPE/PS (1/4) blends.