Plasma-catalytic oxidation of ethyl acetate was conducted in a dielectric barrier discharge (DBD) reactor. The effect of novel nanofiber catalysts (nano-V5Ti and nano-TiO2) and corresponding bulk catalysts on the plasma-catalytic process was investigated and compared with using plasma alone. The combination of plasma and nano-V5Ti catalyst significantly showed the best plasma-catalytic oxidation performance. Catalyst characterization showed that nano-V5Ti possessed smaller crystalline size and higher relative concentration of surface adsorbed oxygen (O-ads) species compared to the bulk catalysts, which played a key role in the enhanced oxidation of ethyl acetate and its intermediates on the catalyst surfaces. Compared to the bulk catalysts, the formation of more reduced vanadium species (V4+) in the nano-V5Ti catalysts indicated the presence of more oxygen vacancies on the nano-V5Ti surface, which in turn improved the reducibility of nano-V5Ti and facilitated surface oxygen species activation in the plasma region and contributed to the plasma-catalytic oxidation reactions.