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Phenethyl-bridged DOPO derivative (DiDOPO) was combined with graphene nanosheets (GNSs) in epoxy resin (EP) to improve its flame retardancy. The results indicated that the introduction of only 1.5 wt％ DiDOPO/1.5 wt％ GNS in EP increased the limited oxygen index (LOI) from 21.8％ to 32.2％, hence meeting UL 94 V-0 rating. The thermogravimetric analyses revealed that char yield rose in presence of GNSs to form thermally stable carbonaceous char. The decomposition and pyrolysis products in gas phase were characterized by thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR), and the release of large amounts of phosphorus was detected in the gas phase. The evaluation of flame-retardant effect by cone calorimetry demonstrated that GNSs improved the protective-barrier effect of fire residue of EP/DiDOPO/GNS. The latter was further confirmed by digital photography and scanning electron microscopy (SEM). Also, Raman spectroscopy showed that GNSs enhanced graphitization degree of the resin during combustion. Overall, the combination of DiDOPO with GNSs provides an effective way for developing high-performance resins with improved flame retardancy.