Electrospun thermoplastic nanofibres were employed to toughen carbon/epoxy composites by direct deposition on carbon fibre fabrics, prior to resin impregnation and curing. The toughening mechanism was investigated with respect to the critical role of phase morphology on the toughening effect in carbon/epoxy composites. The influences of solubility in epoxy and melting characteristics of thermoplastics were studied towards their effects on phase structure and delamination resistance. For the three different thermoplastic nanofibre interlayers used in this work, i.e. poly(epsilon-caprolactone) (PCL), poly(vinylidene fluoride) (PVDF) and polyacrylonitrile (PAN) nanofibre interlayers, only PCL nanofibres produced toughening. Although cylinder-shaped fibrous macrophases existed in all three interlayer regions, only PCL nanofibres had polymerisation-induced phase separation with epoxy, forming ductile thermoplastic-rich particulate microphases on the delamination plane. These findings clearly show that the polymerisation-induced phase separation is critical to the interlayer toughening by thermoplastic nanofibres. An optimal concentration (15 wt.%) of PCL solution for electrospinning was found to produce composites with enhanced mode I interlaminar fracture toughness (G(IC)), stable crack growth and maintained flexural strength and modulus. (C) 2011 Elsevier Ltd. All rights reserved.