Sb 2 O 3 fibrils and tubules with lengths of up to several millimeters and diameters of nanometers to submicrometers were achieved by using Sb 2 S 3 nanopowders as starting material. The synthesis can be ascribed to a vapor-solid process where metal catalyst was neither adopted during the synthesis, nor observed at tips of fibrils or tubules. Sb 2 O 3 fibrils and tubules with lateral dimensions in nano- or submicron-scale may show enhanced catalytic and flame retardant performances.