A new approach employing carbon nanostructure (CNS) buckypapers (BP) was used to prepare glass fiber/epoxy composite materials with enhanced resistance to delamination along with damage monitoring capability. The CNS-BP was subjected to plasma treatment to improve its wettability by epoxy and to promote stronger interfacial bonding. An increase up to 20% in interlaminar fracture toughness in mode I and mode II was observed in composite laminates incorporating CNS BP. Morphological analysis of the fracture surfaces indicated that failure in the conductive CNS layer provided a more effective energy dissipation mechanism, resulting in interlaminar fracture toughness increase. Moreover, fracture of the conductive CNS layer enabled damage monitoring of the composite by electrical resistance measurements upon delamination. The proposed approach provides multifunctional ply interphases, allowing to couple damage monitoring with interlaminar reinforcement of composite laminates.