Amine-cured epoxy resins were modified to improve their impact properties. Urethane prepolymers (PUs), in which terminal isocyanate groups were blocked with nonylphenol (NP) for easy handling, were used as modifiers. The synthesis of the elastomers were carried out at different NCO : OH ratios : 1 : 1, 2 : 1, and 3 : 1 (PU1, PU2, and PU3). Characterization of these materials by GPC and FTIR indicated that PU1 has a negligible amount of NCO-terminated chains and no unreacted toluenediisocyanate (TDI). PU2 and PU3 have free-blocked TDI in the mixture, even after distillation under a vacuum. The molecular weight and polydispersity of the prepolymer increases as PU3 < PU2 < PU1. Copolymerization was carried out by crosslinking with a mixture of cycloaliphatic amines, which react with the epoxy ring and with the NCO groups by deblocking and urea formation. Dynamic mechanical tests were used to measure the glass transition temperatures (T-g) of the copolymers. Two T-g were found if PU1 was the epoxy modifier, indicating that phase separation took place. This was correlated with a structure of PU1 of linear chains with a negligible amount of reactive groups. Flexural and compression properties showed negligible changes for PU2- and PUB-modified epoxy, but the critical strain energy release rate (G(1C)) was improved if PU2 was the modifier. This behavior was explained by the Linkage of elastomeric chains into the epoxy network. The PU1-epoxy copolymer showed a completely different behavior, with the bending modulus (E-b) reduced to almost one-half with respect to that of the epoxy matrix and with largely improved impact properties. This difference was attributed to the separation of an elastomeric phase, which favors the formation of shear bands in the epoxy matrix.