Nanocrystalline barium hexaaluminate has been successfully synthesized through the use of a reverse microemulsion as a medium for controlled hydrolysis and polycondensation of barium and aluminum alkoxides. The nanoparticles derived were characterized with electron microscopy, X-ray diffraction, and nitrogen adsorption analysis. This novel material possessed a well-defined particle morphology and an ultrahigh surface area, and exhibited excellent catalytic performance in methane combustion. Its structural evolution was found to be strongly dependent on synthesis parameters, such as water/alkoxide ratio and aging period. Powder recovery and drying techniques also had an important impact on particle agglomeration and structural development. Through the unique synthesis approach described, barium hexaaluminate with superb thermal stability was achieved, with surface areas in excess of 100 m(2)/g retained even after calcination at 1300 degrees C.