Tin oxide (SnO2) microspheres with an average 2.5 mu m in diameters have been successfully synthesized through a rapid hydrothermal process heating by microwave in the presence of an ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate. X-ray diffraction, scanning electron microscopy and transmission electron microscopy are used to characterize the morphology and crystalline structure of the microspheres. The as-synthesized SnO2 microspheres exhibit a tetragonal rutile structure. The mechanism of the microspheres formation is proposed. (c) 2007 Elsevier Inc. All rights reserved.