Unique trilayer (TL) thin films of sodium montmorillonite (MMT), poly(allylamine hydrochloride) (PAH) and poly(sodium phosphate) (PSP) are prepared via layer-by-layer (LbL) assembly. This three-component nanocoating completely shuts down melt dripping and reduces heat release of open-celled flexible polyurethane (PU) foam when exposed to direct flame due to a synergistic interaction between PSP and the thermally shielding clay platelets in the condensed phase. Post burn scanning electron microscopy reveals the nanocoating's swollen morphology is able to maintain foam shape, cellular structure, and porosity. Cone calorimetry reveals that 4 TL coated foams (<3 wt% addition) have a peak heat release rate that is reduced by 54% relative to the uncoated control. Using LbL assembly, this work combines two common flame-retarding mechanisms (thermal shielding clay and intumescing PAH/PSP) in a single coating system and provides a foundational platform for new environmentally-benign flame retardant strategies for various substrates (e.g., foam found in home furnishings).