PEG coils have been exploited as chemical template to fabricate hollow Sb2O3 microspheres in water-ethanol solution at room temperature. The obtained hollow Sb2O3 microspheres were in the range of about 50-200 nm in diameter, and the shell were in the range of obout 10-20 nm in thickness. In the method, the formation of a certain sized hydrating PEG coil is crucial step, which is related with the process orders.