Abstract In this article, we report on a controllable synthesis of superhydrophobic Sb₂O₃ microcrystals via a solvothermal method assisted with the soluble inorganic Na₂WO₄ salt. Morphologies of the final products depend on the amount of the OH⁻ ions adsorbed on Sb₂O₃ nanoplates. By varying the amount of NaOH, the octahedral Sb₂O₃ can be switched to microcrystals or microspindles. Reaction and formation mechanisms of Sb₂O₃ were also proposed, which may also benefit synthesis of other metal oxides with controllable morphology. Additionally, after modified by (Heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane, the as-synthesized octahedral Sb₂O₃ microcrystals and Sb₂O₃ microspindles show superhydrophobic and excellent anticorrosion properties in acidic and basic circumstances.