Poly-etherether-ketone (PEEK) fibres (average diameter 30μm) were surface-activated by a UV-irradiation technique, and then used as interlayers of carbon fibre/epoxy composites. The results of a flatwise tensile test demonstrated a significant improvement in the PEEK fibre/epoxy adhesion upon the UV-treatment, i.e. the ultimate strength increased from 0.6–0.7MPa to 7.6MPa. Accordingly, interlaying UV-irradiated PEEK fibres resulted in considerable increases in the maximum values of open-hole tensile strength, Charpy impact strength and mode-I fracture energy, i.e. of 12%, 131% and 293%, respectively. However, it also decreased the flexural strength by 29%, owing to the thickness increase caused by adding interlayers. Fortunately, the load carrying capacity (the maximum failure load under flexural bending) was largely unaffected, and moreover, an average residual strength of 475 ± 23MPa still remained after the damage at the maximum load. The results demonstrated significant benefits of using longitudinal UV-irradiated PEEK fibres as interlayers of CFRPs.