In this work, GO was functionalized by a hyper-branched flame retardant, which was synthesized by the reaction of N-aminoethyl piperazine and di(acryloyloxyethyl)methylphosphonate. Subsequently, the resultant functionalized GO (FGO) was incorporated into the cross-linked polyethylene (XLPE) to enhance the flame retardancy of the matrix. Transmission electron spectroscopy images indicated that FGO exhibited uniform dispersion in XLPE matrix and strong adhesion with the matrix by cross-linking, which improved barrier effect due to reduced heat release and the free radical transfer between the matrix and graphene nanosheets. The incorporation of FGO into XLPE matrix endowed polymer composites with flame retardancy and thermal stability. In addition, the homogeneous dispersion of functionalized GO with a hyper-branched flame retardant in the polymer matrix improved the antioxidation and mechanical properties of XLPE-FGO nanocomposites compared to the XLPE-GO samples, as demonstrated through the oxidative induction temperature and time test, oven aging test and mechanical test.