We have studied the preparation of a new class of epoxy thermosets from diglycidyl ether of bisphenol A (DGEBA) modified with an amphiphilic star polymer (SP), initiated either by 1-methyl imidazole or ytterbium triflate, anionic and cationic initiators, respectively. The curing process has been characterized by means of DSC, FTIR and rheology. The last technique allowed us to monitor the shrinkage during curing. DMTA provided valuable information about the transitions of the materials, as well as their modulus in the rubbery state. Cationic systems produce monomodal tan 6 relaxations, whereas anionics presented a shoulder in this peak. By means of electron microscopy we could observe phase separation in the case of cationically initiated systems while in the anionic initiated materials zones with different electronic densities were appreciated. Finally. Young's modulus and hardness of the materials were determined by nanoinentation. (C) 2011 Elsevier Ltd. All rights reserved.