Core/shell structures have been prepared via a mechanofusion system by employing several kinds of spherical polymers as a core material and Al2O3 powder or a mixture of Al2O3 and SiO3 powders as a shell material. The effect of the kind of core polymers on the quality of the resulting hollow alumina microspheres has been discussed on the basis of the thermal decomposition behavior of spherical polymers used as a core material. A large fraction of hollow alumina microspheres reflecting the shape and the particle size distribution of the core polymer could be fabricated after sintering at 1600degreesC for 3 h, when highly cross-linked poly(methyl methacrylate) (PMMA) microspheres with a gel fraction of 99.03% were used as a core polymer, and abrupt firing at temperatures higher than 500degreesC was adopted to remove the PMMA microspheres. The addition of 5 mass% SiO2 to the Al2O3 shell layer was found to be useful for maintaining the spherical shell structure during the firing process and for fabricating a large fraction of hollow alumina microspheres after the sintering.