Abstract: Based on interfacial polymerization reaction, PSRF double shell microspheres were synthesized by using polystyrene （PS） hollow microspheres as template, RF as precursory solution and dibutyl phthalate as dispersant. Then basing on the former step, RF hollow microsphere was cranked out through throwing off template, which was done through acetone. The component, morphology, aperture, and surface roughness of RF hollow microsphere were characterized by infrared spectrum, Xray, TEM, AFM and nitrogen adsorptiondesorption, respectively. The results show that RF hollow microsphere is monolayered hollow sphere, and has a typical structure of the porous aerogel, and consists of particle size about 10 nm and uniform particle size distribution of nanoparticles pose, and its average aperture is about 17 nm. The sphericity and concentricity of the monolayer hollow microsphere are higher than 95%, and the surface finish is less than 10 nm, which satisfies all the requirement of instantlighted firebrand.