Low molar mass hydroxyl-terminated polyester was functionalized with isocyanate groups (NCO) and used to improve the impact resistance of epoxy resin (ER) cured with triethylene tetramine (TETA). The effect of polyester-based modifiers (with or without NCO groups) on the curing rate of epoxy/TETA system was investigated by rheological techniques. It was found that the functionalized polyester decreased the gel time, indicating an accelerating effect of the curing process. In addition, significant improvement in impact resistance of the epoxy network was achieved, with low detrimental effect on the glass transition temperature and stiffness. The modified epoxy systems did not present phase-separated morphology discernible by scanning electron microscopy, even after the curing process. The glass transition temperature of the epoxy networks was also investigated by dynamic-mechanical analysis.