A novel flame retardant poly(vinyl alcohol) (PVA)/melamine polyphosphate (MPP)-graphene nanocomposite has been prepared by solvent blending. Results from X-ray diffraction (XRD) and transmission electron microscopy (TEM) suggest that an excellent dispersion of exfoliated graphene and MPP in the PVA matrix was achieved. The thermal and flammability properties of the nanocomposite were investigated using thermogravimetry, cone calorimetry, and flammability tests (UL 94 and LOI). The presence of both MPP and graphene in the polymer matrix led to an enhanced thermal stability and significantly reduced flammability for the nanocomposite. PVA composites filled with 10 wt% MPP and 1 wt% graphene ( PVA/G1/MPP10) achieved the LOI value of 29.6 and UL-94 V0 grade. Compared to pure PVA, the peak heat release rate (PHRR) of PVA/G1/MPP10 is reduced by about 60%. Meanwhile, the mechanical properties of PVA/G1/MPP10 composites exhibit almost no deterioration compared with pure PVA. The morphology and composition of residues generated after cone calorimeter tests were investigated by scanning electronic microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The SEM images showed the compact and dense intumescent char jammed with graphene sheets was formed for PVA/G1/MPP10 during combustion. The results of XPS confirmed that carbon content of the char for PVA/G1/MPP10 is increased obviously by the combination effect of the flame retardant MPP and graphene. (C) 2011 Elsevier B.V. All rights reserved.