An elaborate survey of the chemical modification methods for endowing highly flammable SBS with increased fire resistant properties by means of chemical modification of the polymer backbone with phosphorus containing fire retardant species is presented. Optimal conditions for free radical addition of the Psingle bondH containing fire retardants to a double bonds of poly(butadiene) block of SBS were found, affording varied degree of the modification (0.2–21 mol%). Alternatively, a two-step procedure based on an epoxidation step followed by hydrolysis of the epoxides with phosphoric acid was developed resulting in 20 mol% of poly(butadiene) block modification. Based on TGA results, organophosporus-modified SBS was found to be amenable to charring – a property which correlated directly with the reduced flammability of the modified polymer observed in Cone Calorimetry tests. Furthermore, conceptually novel application of the H3PO4 modified SBS as a fire retardant additive for bitumen material, in combination with synergetic melamine species, offered 25% better self-extinguishing properties of such formulation already at a low loading level of the fire retardant components (3.5 wt.%).