To functionalize the surfaces of graphene oxide (GO) and improve its interfacial compatibility to polymers, the nanosheets of nickel phyllosilicate (Ni-PS) self-assembly decorated on GO (GO@Ni-PS) were first synthesized via the combination of one-step solgel and gentle hydrothermal approaches. Then, the as-synthesized GO@Ni-PS was incorporated into epoxy resin (EP) as filler to yield high-performance composites. By structural, morphological and thermal characterizations, we found the GO@Ni-PS has been successfully synthesized and could disperse homogeneously in the EP matrix. The added GO@Ni-PS depicts the positive influences on the thermal stabilities, tribological properties as well as the flame retardancy in high heat flux. Also, the excellent accelerating influence of GO@Ni-PS on the curing behavior of EP was presented and the kinetic analysis quantitatively demonstrated the gradually decreased activation energy of curing along with increased GO@Ni-PS content.