Polyurethane foam (PUF) is widely used in building insulation field but highly flammable. In an effort to develop an efficient way to reduce flammability and smoke release of PUF without sacrificing its inherent merits, a novel strategy has been proposed to decorate silica aerogels onto the surface of PUF to fabricate hierarchically porous SiO2/PUF composites. Due to the unique hierarchically porous structure, the resultant composites showed superior thermal insulation with a lower thermal conductivity of 0.0282 W/(m K). The introduction of silica aerogels also effectively improved the compressive strength, almost 220% of that of neat PUF. Notably, the SiO2/PUF composites were rendered self-extinguishing in vertical burning tests and had a high limiting oxygen index (WI) value of 32.5%. Cone calorimetry (CC) tests revealed that the peak heat release rate (PHRR) and peak smoke production release (PSPR) of theSiO(2)/PUF composites were reduced by 40.4% and 45.6%, respectively. Particularly, the specific optical density (Ds) of the composites displayed as 55.7% reduction in the smoke density chamber tests, showing excellent smoke-suppression. The mechanism analysis suggested that a compact silica-rich hybrid barrier formed, preventing thermal degradation products and energy transfer during combustion. These results indicate SiO2/PUF composites have enormous potential as building insulation materials.