Mixtures of epoxy resins in the presence of epoxy hyperbranched polymers (HBP), in the range of 5-15 wt%, were investigated in the cationic photocuring process. No significant differences in rate of polymerization or final epoxy groups conversion were observed. At low concentration, HBP acts as plasticizer and causes a decrease of the glass transition temperature of the epoxy matrix and of the E' value. At higher concentration (about 15 wt%), two T-g values are evident, indicating a biphasic structure of the system. The SEM analysis of the fracture surface of the samples confirms a particulate structure with separate HBP domains interconnected to the epoxy matrix. In all the samples investigated, a clear increase of the impact resistance was observed, resulting either from the plasticization effect or from the particulate structure induced by the presence of the HBP resin.