A novel epoxy/SiO2 hybrid sizing for carbon fiber surface was prepared through sol-gel technique, the structure of the sizing were analyzed, and the effects of the sizing on mechanical properties of carbon fiber composites were also investigated. The analyses by FT-IR and SEM indicated that epoxy/SiO2 hybrid sizing was prepared successfully, SiO2 particles dispersed in the hybrid sizing film homogeneously with nanoscale. The analyses on interlaminar shear strength (ILSS) and impact properties of composites showed that the epoxy/nano-SiO2 hybrid sizing increased ILSS and improved impact properties obviously at the same time.