Hyperbranched polyurethane (HBPU), with low-molecular-weight polyethylene glycol space segments between the branching points, was synthesized by a pseudo one-pot procedure. HBPU was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The HBPU was used as a modifier of diglycidyl ether of bisphenol A (DGEBA)/anhydride system. The rheological properties of HBPU-G3/DGEBA blends were investigated by rotational rheometer. A slight decrease in viscosity of modified blends was observed by adding low content of HBPU and there was chemical reaction between HBPU and epoxy resin even without a hardener. The mechanical and thermal properties of the HBPU-G3/DGEBA thermosets were characterized and compared with that of the neat epoxy thermosets. Their impact fracture surfaces were investigated by scanning electron microscopy, and the results indicated that no phase separation occurred in the DGEBA/anhydride system after the introduction of HBPU, which was confirmed by dynamic mechanical analysis and thermogravimetric analysis. After addition of 10 wt % HBPU, the toughness of the modified thermosets was found to be significantly improved without sacrificing their processability and thermal and mechanical properties to a large extent. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40614.