A series of novel reactive toughening agents (LCEUPPG) containing both a flexible spacer and rigid liquid crystalline unit were synthesized to modify the bisphenol epoxy resin/dicyandiamide curing system. The curing reactivity, apparent activation energy, curing mechanism, dynamic mechanical behavior, and impact strength of the modified system were systematically studied. Compared with the unmodified system, the results indicate that LCEUPPG have greatly accelerated the curing reaction between epoxy resin and dicyandiamide, reduced the apparent activation energy of the curing reaction, enhanced the impact strength 3-7 times, and maintained high dynamic modulus and good thermal properties. In addition, SEM observation of the fracture surfaces showed a two-phase microstructure in the modified systems.