Here, a long-term anti-corrosive epoxy (EP) coating based on nano-hybrid filler was developed. The surfaceof graphene oxide (GO) was aminated with (3-aminopropyl) triethoxysilane (APTES), and then theporous covalent organic framework (COF) was in-situ grown on amino functionalized graphene oxide(FGO) nanosheets by Schiff-based reaction to prepare FGO-COF nanofillers. Different characterizationmethods proved the successful modification of GO nanosheets with COF particles. The excellent waterresistance of composite coatings was characterized through contact angle, adhesion, and water uptaketests. Transmission electron microscope (TEM) and molecular dynamics (MD) methods showed thatthe grafting of COF enhanced the dispersion and compatibility of GO in the coating. EIS measurements,salt spray analysis and cathodic delamination test indicated the significant improvements in the protectiveproperties of the composite coatings compared with pure EP coating. The low-frequency impedancemodulus of 1% FGO-COF composite coating reached higher than 6.8 109 Xcm2 after immersed in seawater for 60 days. In addition, the 1% FGO-COF composite coating performed only 34% delamination ratioafter 120 h cathodic delamination test.