A novel hybrid flame retardant combining graphene oxide (GO) with long-chain phosphaphenanthrene was fabricated via surface grafting reaction. Taking advantageous of the double barrier effects, including the physical shield contributed by graphene nanoplates during the initial stage and the chemical char contributed by phosphaphenanthrene during the later stage, greatly decreased the release rate of decomposed volatiles from the resin, as well as minimized the release of oxygen and combustion heat. Hence, such hybrid flame retardant can overcome the shortcomings of early acid catalyzed degradation effects caused by conventional flame retardants containing phosphorus. Satisfactory flame retardance was achieved (UL94 V-0 rating) with only 4% addition of the hybrid flame retardant to the epoxy resin laminate. Due to the long-chain and bulky phosphaphenanthrene groups, the interlayer attractive forces of the modified GO were effectively weakened, thus favoring the exfoliation and dispersion of graphene sheets. As a result, the incorporation of the flame retardant slightly enhanced the mechanical properties of the polymer composites, rather than deteriorating them, as occurs with traditional additive flame retardants. As a potential application for graphene, it is believed that the reported hybrid flame retardant has promising future prospect.