The use of halogen-based materials has been regulated since toxic substances are released during combustion. In this study, polyurethane foam was coated with cationic starch (CS) and montmorillonite (MMT) nano-clay using a spray-assisted layer-by-layer (LbL) assembly to develop an eco-friendly, high-performance flame-retardant coating agent. The thickness of the CS/MMT coating layer was confirmed to have increased uniformly as the layers were stacked. Likewise, a cone calorimetry test confirmed that the heat release rate and total heat release of the coated foam decreased by about 1/2, and a flame test showed improved fire retardancy based on the analysis of combustion speed, flame size, and residues of the LbL-coated foam. More importantly, an additional cone calorimeter test was performed after conducting more than 1,000 compressions to assess the durability of the flame-retardant coating layer when applied in real life, confirming the durability of the LbL coating by the lasting flame retardancy.