Flexible polyurethane foam (PUF) is widely used in bedding, transportation, and furniture, despite being highly flammable. In an effort to decrease the flammability of the polymer, an environmentally friendly flame retardant coating was deposited on polyurethane foam (PUF) via layer-by-layer assembly. Treated foam was subjected to three different fire scenarios, 10 s torch test, cone calorimetry, and a 900 s burn-through test, to evaluate the thermal shielding behavior of an eight bilayer chitosan/vermiculite clay nanocoating. In each fire scenario, the nanocoating acts as a thermal shield from the flames by successfully protecting the backside of the PUF, whereas the side directly exposed to the flame results in a hollowed nanocoating that maintains the complex three-dimensional porous structure of the foam. Cone calorimetry reveals that the coating reduces the peak heat release rate and total smoke release by 53 and 63%, respectively, whereas a temperature gradient greater than 200 °C is observed across a 2.5 cm thick coated foam sample during the rigorous burn-through fire test. The thermal shielding behavior of this polymer/clay nanocoating makes this system very attractive in improving the fire safety of polyurethane foam used for insulating applications.