In this study, an aerospace thermosetting composite was co-curing joined by Polyether-ether-ketone (PEEK) and Polyethylenimine (PEI) films, with an aim of developing advanced composite joints. The semi-crystalline PEEK films were surface activated upon a UV-irradiation technique to obtain a strong film–composite interface, while the amorphous PEI films could be directly used. The fracture behaviour of the composite joints was evaluated and compared with benchmark aerospace adhesive joints. The experimental results proved remarkable mode-I and mode-II fracture resistance of the PEEK co-cured joints at 22 °C and 130 °C, while the PEI co-cured joints exhibited excellent mode-I fracture resistance at 22 °C and mode-II fracture resistance in both testing temperature cases. Extensive elongation, tearing and fracture of the PEEK/PEI plastics were proved to be the main mechanisms for toughness enhancement. Overall, this work had successfully demonstrated the effectiveness of developing advanced composite joints via a co-curing process using high-performance thermoplastic films.