In this study, the preparation of modified graphene oxide (GO) synergistic structure (ZSM-5-NH-GO) and the effect of this structure on the corrosion performance of epoxy coatings were investigated. The structural and morphological properties of ZSM-5-NH-GO were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The corrosion performances were studied by electrochemical impedance spectroscopy (EIS) and salt spray tests. The EIS results showed that the corrosion resistance of steel substrate was considerably improved by ZSM-5-NH-GO. The salt spray tests demonstrated that the ZSM-5-NH-GO coating provided strong corrosion performance for steel substrate. The mechanical properties of the epoxy-composite coatings containing ZSM-5-NH-GO were studied by adhesion tests. The above results indicated that the composite coating containing 0.7 wt % ZSM-5-NH-GO composite possessed most excellent anti-corrosion performance compared with other epoxy coatings.