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A comparative study between graphene and modified graphene oxide (mGO) on the flame retardancy of graphite doped intumescent flame retardant (IFR) coatings is preliminarily investigated by cone calorimeter (CC), XRD, and SEM, with the final aim of clarifying the interactions between different graphenes and graphite doped coatings (polyester resin-ammonium polyphosphate-urea-pentaerythritol). The CC results determine that graphene exerts an obviously antagonistic effect on flame resistance, evidenced by the increased peak heat release rate (p-HRR) of 56.9 kW·m−2 for SD8+graphene (sample coating contains graphite with a particle size of 8 μm and 0.5 wt.% graphene as dopant), which increased by 80.6% compared with SD8 (coating contains graphite with a particle size of 8 μm); substitution with graphene or mGO imparts an acceleration of fire growth, because graphene inertness improves the viscosity of melting system, evidenced by the cracked appearance and porous structure of SD8+graphene. However, the higher reactivity of mGO favors the combustion; the barrier effect inhibits the transfer of mass and heat simultaneously, leading to a slight influence on flame retarding efficiency.