A series of novel chain-extended ureas (U-i) containing poly(ethylene glycol) (PEG) spacers with different molecular weights were synthesized and the reactive mechanism, reactive activity, impact strength, dynamic mechanical behavior, morphology, and storage properties of the epoxy resin/chain-extended urea system were studied. Experimental results revealed that the impact strength of the epoxy resin modified with chain-extended urea containing a PEG flexible spacer with molecular weight of 1000 is 9.5 times higher than that of the epoxy resin/dicyandiamide system. Results also show that the molecular weight of PEG in chain-extended ureas hardly has any influence on the reactive activity of the chain-extended ureas. The storage life of the epoxy resin/U-i system can be delayed to 38 h at 50 degrees C.