The polymerization of styrene in the presence of graded block copolymers with a polystyrene/polybutadiene composition of 40/60, 30/70, and 20/80 and with a polydispersity index ((M) over bar (w)/(M) over bar (n)) in the polystyrene block varying from 1.1 to 1.6 was studied. As the polydispersity index of the polystyrene block increases, an improvement of up to 50% in the Iod impact toughness of the produced high-impact polystyrene was achieved. The rubber particle morphology type, the size, and the volume fraction of the rubber phase particles could be modified through changes in the composition of the graded block copolymer. The changes that occurred in the rubber phase were mainly generated by the variation in the interfacial tension between the phases, and this variation was principally attributed to an increase in the polydispersity index of the polystyrene block in the precursor copolymer.