Epoxy-amine networks with a nanodomain toughener-soft nanostructured ether-crosslinked domains (NECDs), which could increase the fracture and tensile toughness of the networks, were simply obtained when a mixture of diglycidyl ether bisphenol A (DGEBA) epoxy resin and 4,4'-methylene dianiline (MDA) hardener was heat-cured in the presence of varying amounts of the imidazole derivatives (called imidazoles)-1-methylimidazole (1-MI) or 2-methylimidazole (2-MI). Under these conditions, the epoxide groups in DGEBA underwent not only polyaddition with the aromatic amine of the MDA to form a hard epoxy-amine networked matrix but also anionic ring-opening polymerization by itself to build soft NECDs connected to the epoxy-amine matrix. The curing chemistry of the DGEBA/MDA mixture, both with and without the imidazoles, was studied using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The morphology of the networks dispersed with 5-30-nm-sized NECDs was investigated by atomic force microscopy (AFM). When the optimum amount (similar to 0.15-0.30 wt%) of imidazoles was added, the NECDs were effective in significantly increasing the tensile and fracture toughness and the thermal stability of the epoxy-amine networks without markedly sacrificing the glass transition temperature (T-g). The novel toughening mechanism and thermal behavior of the epoxy-amine networks were discussed. (c) 2011 Elsevier B.V. All rights reserved.