The graphene oxide modified epoxy resin curing agent (TGO-WPEA) is synthesized by situ polymerization method which firstly form a covalent bond between triethylenetetramine (TETA) and graphene oxide (GO) by ball milling, and then epoxy resin E44, trihydroxymethyl propane triglycidyl ether (TPEG), Methyl polyoxyethylene epoxy ether (MEH) and γ-(2, 3-propylene oxide) propyl trimethoxy silane (KH560) are added successively. Graphene oxide modified waterborne epoxy resin anti-corrosion coating (TGO-EP) is prepared by the combination of TGO-WPEA and epoxy resin emulsion (Epikote-6520). The structure of TGO nanomaterials is characterized by FTIR, XPS and XRD. The corrosion resistance of the composite coating is characterized by electrochemical test and salt spray test, and the physical properties of the coating are tested. The results showed that: the curing agent molecules are covalently linked to the GO surface and the layer spacing of GO is improved. The TGO-EP composite coating prepared by intercalation polymerization has higher anti-corrosion performance. Compared with the pure EP coating, the corrosion potential of TGO-EP composite coating is increased from -0.267 mV to -0.125 mV. The corrosion current density decreased from 5.44×10-8 to 1.09×10-8 A/cm2. The EIS test showed that TGO-EP still had the highest impedance radius and no quadratic time constant after 20 days of immersion.