ZnO inverse opals are fabricated by electrophoresis of polystyrene (PS) microspheres (720 nm in diameter) on a ITO glass to form a close-packed colloidal crystal, followed by potentiostatic deposition of ZnO in the interstitial voids among the PS microspheres and chemical removal of the PS colloidal template. By adjusting the electrodeposition time, we obtain semi-layered and multi-layered ZnO inverse structures with significantly reduced defects and considerable surface uniformity. The semi-layered ZnO inverse opals display a bowl-like morphology with individual cavities isolated from each other. In contrast, the multi-layered ZnO inverse opals exhibit a three-dimensional skeleton with hexagonally-arranged cavities interconnected to each other. After surface coating of perfluorodecyltriethoxysilane, both samples reveal a superhydrophobic nature with contact angle larger than 150 degrees. In electrowetting measurements, the contact angles are decreasing with increasing applied voltages. The droplet on the semi-layered ZnO inverse opals demonstrates a notable transition from the Cassie-Baxter state to the Wenzel one. However, the droplet on the multi-layered ZnO inverse opals indicates three distinct regimes; Cassie-Baxter state, mixed Cassie-Baxter/Wenzel state, and Wenzel state. Repelling pressure of the entrapped air in the cavities is estimated to explain the observed contact angle variation upon the applied voltage for both samples. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3594723] All rights reserved.