AbstractDelamination is a common failure mechanism affecting composite laminates. Thermoplastic poly(ethylene oxide) (PEO) nanofibers are recently proposed for toughening carbon fiber reinforced polymers (CFRPs), obtaining promising results. In the present work, PEO‐modified epoxy CFRPs underwent ageing in water for 1 month, and the interlaminar properties are assessed via double cantilever beam (DCB) and end‐notched flexure (ENF) tests. The Mode I delamination behavior of both PEO‐modified and unmodified commercial composite plates is compared. Water ageing slightly affects the mechanical properties of the nano‐modified laminates, though the interleaved nano‐reinforcement is water‐soluble. The achieved results are very encouraging and pave the way to the use of PEO nanofibrous mats for hindering delamination in composite laminates.