As a novel and efficient halogen-free composite flame retardant, zinc borate (4ZnO center dot B2O3 center dot H2O)/reduction graphene oxide (RGO) hybrid material (ZB/RGO) was designed and synthesized using a facile route involving nano-engineering. The unique structure and composition of ZB/RGO were efficaciously confirmed by XRD, FTIR, SEM, TEM, and TG. The incorporation of 7.71 wt% ZB/RGO could significantly enhance the synergistic effect with Mg(OH)(2) (MH) when mixed with poly(vinyl chloride) (PVC) as a flame retardant and smoke suppressant, as evaluated by limited oxygen index (LOI), microscale combustion calorimetry (MCC), and a cone calorimetry test (CCT) and compared with PVC, PVC/ZB, PVC/MH, and PVC/ZB/MH blends. The PVC/ZB/RGO/MH formulation could achieve an LOI value of 29.5% (24% higher than neat PVC). More importantly, the heat release rate (HRR), peak heat release rate (PHRR), smoke production rate (SPR), perk smoke production rate (PSPR), total smoke production (TSP), and mass amount loss (MAL) were considerably reduced in CCT, especially the PHRR, TSP, and MAL values for PVC/ZB/RGO/MH blends were reduced to 35%, 34%, and 15%, respectively. This study showed that the design of the novel material might provide a reference for the future development of halogen-free flame retardants consisting of inorganic salt and carbon material, which exhibit excellent flame retardant and smoke suppressant behavior. (C) 2017 Elsevier B.V. All rights reserved.