This paper reports preparation of polymer aerogel microparticles via sol-gel reactions inside micrometer size droplets created in an oil-in-oil emulsion system. The oil-in-oil emulsion system is obtained by dispersing in cyclohexane the droplets of the sols of polybenzoxazine (PBZ) or polyimide (PI) prepared in dimethylformamide. The sol droplets transform into harder gel microparticles due to sol-gel reactions. Finally, the aerogel microparticles are recovered using supercritical drying of the gel microparticles. The PBZ and PI aerogel microparticles prepared in this manner show mean diameter 32.7 and 40.0 μm, respectively, mesoporous internal structures, and surface area 55.4 and 512.0 m(2)/g, respectively. Carbonization of PBZ aerogel microparticles maintains the mesoporous internal structures but yields narrower pore size distribution.