A durable and flexible silicone-based backcoating (halogen free) is applied to the backside of an otherwise smoldering-prone and flammable fabric. When exposed to fire, cyclic siloxanes (produced by thermal decomposition of the backcoating) diffuse through the fabric in the gas phase. The following oxidation of the cyclic siloxanes forms a highly conformal and thermally stable coating that fully embeds all individual fibers and shields them from heat and oxidation. As a result, the combustion of the fabric is prevented. This is a novel fire retardant mechanism that discloses a powerful approach towards textiles and multifunctional flexible materials with combined smoldering/flaming ignition resistance and fire-barrier properties.