AbstractThe effects of rubber particle size and rubber/matrix adhesion on the impact properties of a brittle polymer have been separated using polystyrene (PS)/acrylonitrile‐butadiene rubber (NBR) as a model system in which interfacial chemical reaction could be controlled. It has been proven that the interfacial adhesion between the rubber phase and the PS matrix not only greatly aids in reducing the rubber particle size but also plays a further role in improving the impact properties of the matrix polymer. The impact energies of PS/NBR blends with interfacial chemical bonding are four to ten times as high as those without interfacial bonding for the same average rubber particle size. However, at temperatures below the glass transition temperature of the rubber, there is no difference in impact energies with or without interfacial chemical bonding. It has been found that the optimum rubber particle size for toughening PS is influenced by interfacial adhesion. Smaller optimum rubber particle size is observed for blends with greater amounts of interfacial chemical bonding.