We here propose a simple, facile, and effective method to prepare submicron mullite hollow spheres templated from Pickering emulsions. Dual-phase sol consisted of boehmite and silica nanoparticles decorated by pentanoate ion could assemble at water/oil interface irreversibly to form photosensitive Pickering emulsions. The droplets of emulsions could be separated by dilution and formed by photopolymerization to gain hybrid microspheres, which could completely transform to mullite hollow microspheres via binder removal and sintering. It is found that the prepared hollow microspheres possess intact morphology, favorable sphericity, large cavity volume, and bulk density of 0.356 g/cm 3 . Importantly, the average diameter of mullite hollow spheres obtained via this method could be as low as 0.33-2.31 μm. This steady method is efficient and suitable for various types of inorganic particles, providing an innovative perspective for preparing fine hollow spheres applicable for filtration, drug loading as well as energy storage areas.