Thermoset composite toughening by interleaf materials receives increasing attention as requirements for high toughness become essential for primary structures. Here, polyphenylene oxide (PPO) electrospun veils were used for carbon fiber epoxy composite interleaf toughening. Their Mode I, Mode II interlaminar fracture toughness (GIC and GIIC) were measured as a function of veil loading levels. 10 wt% veil loading rendered the best toughening performance, reached to 530 J/m2 and 1400 J/m2 in GIC and GIIC, respectively, and it yielded further increase of 140% and 30% compared to the corresponding PPO particles. Scanning electron microscopy (SEM) and 3-D laser microscopic imaging analysis (3D-LMIA) on fracture surfaces revealed energy absorbing mechanisms such as bridging and plastic deformation. The continuous network structure imparted by the veils accounted for the additional toughening mechanisms, i.e. the deformation, breakage and pull-out of PPO fibers, that were responsible for the outstanding fracture toughness.