Recent discoveries of two-dimensional transitional metal based materials have emerged as an excellent candidate for fabricating nanostructured flame-retardants. Herein, we report an eco-friendly flame-retardant for flexible polyurethane foam (PUF), which is synthesised by hybridising MXene (Ti[Formula: see text]) with biomass materials including phytic acid (PA), casein, pectin, and chitosan (CH). Results show that coating PUFs with 3 layers of CH/PA/Ti[Formula: see text] via layer-by-layer approach reduces the peak heat release and total smoke release by 51.1% and 84.8%, respectively. These exceptional improvements exceed those achieved by a CH/Ti[Formula: see text] coating. To further understand the fundamental flame and smoke reduction phenomena, a pyrolysis model with surface regression was developed to simulate the flame propagation and char layer. A genetic algorithm was utilised to determine optimum parameters describing the thermal degradation rate. The superior flame-retardancy of CH/PA/Ti[Formula: see text] was originated from the shielding and charring effects of the hybrid MXene with biomass materials containing aromatic rings, phenolic and phosphorous compounds.