The present study describes the effect of the macromolecular modifications on the fracture toughness of an epoxy system. We synthesized epoxy networks by the reaction of diglycidyl ether of bisphenol A (DGEBA) with methyl-tetrahydro-phthalic anhydride (MTHPA), initiated by a tertiary amine. Several materials were obtained by adding a high molecular weight monomer to one with low molecular weight (both based on DGEBA) at different concentrations. In every case, a stoichiometric amount of MTHPA was employed. The glass transition temperature and the Angell's fragility index, derived from thermo-viscoelastic properties, were used to characterize the materials. Relationship between these two parameters and the fracture properties, including the fracture toughness and the microscopic roughness of the fracture surfaces observed by atomic force microscope (AFM), was then investigated. We found that there were direct correlations among the glass transition temperature, the fragility, the fracture toughness, and the roughness. This study revealed that both the glass transition temperature and the fragility are effective for characterizing material in relation to the fracture toughness of the blended epoxy resins.