Core–shell particles (CSPs) were prepared by hyperbranched polyesters (HBPs), which synthesized by the polycondensation of succinic anhydride and diethanolamine, grafted on zirconium slag nanoparticles (ZSN), a kind of solid waste in zirconium industry. The CSPs were characterized by attenuated total internal reflectance infrared spectroscopy (ATR‐IR), nuclear magnetic resonance spectroscopy (NMR), high resolution transmission electron micrographs (HRTEM), and thermogravimetric analysis (TGA). Then the effect of CSPs on impact enhancement of epoxy resin thermosets modified by HBP with different kinds of functional terminal groups, such as hydroxyl group, epoxide group, and amino group, was studied. The results indicated that the addition of CSPs resulted to a strong interfacial adhesion and thus improve the impact resistance of epoxy resin thermosets. POLYM. COMPOS., 38:441–451, 2017. © 2015 Society of Plastics Engineers