The synergistic effect of conventional flame-re-tardant elements and graphene has received extensive attention in the development of a new class of flame retardants. Compared to covalent modification, the non-covalent strategy is simpler and expeditious and entirely preserves the original quality of graphene. Thus, non-co-valently functionalized graphene oxide (FGO) with a phosphorus-nitrogen compound was successfully prepared via a one-pot process in this study. Polyethyleneimine and FGO were altatively deposited on the surface of a poly(vinyl alcohol) (PVA) film via layer-by-layer assembly driven by electrostatic interaction, imparting excellent flame retardancy to the coated PVA film. The multilayer FGO-based coating formed a protective shield encapsu-lating the PVA matrix, effectively blocking the transfer of heat and mass during combustion. The coated PVA has a higher initial decomposition temperature of about 260 °C and a nearly 60％reduction in total heat release than neat PVA does. Our results may have a promising prospect for flame-retardant polymers.