Interaction of water on heterogeneous nonwetting interfaces has fascinated researchers' attention for wider applications. Herein, we report the evolution of hierarchical micro-/nanostructures on superhydrophobic pseudoboehmite surfaces created from amorphous Al2O3 films and unraveled their temperature-driven wettability and surface energy properties. The influence of hot water immersion temperature on the dissolution-reprecipitation mechanism and the surface geometry of the Al(2)O(3 )film have been extensively analyzed, which helped in attaining the optimal Cassie-Baxter state. The evolution of pseudoboehmite films has been structurally characterized using grazing incidence X-ray diffraction, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy and atomic force microscopy. Interfacial surface energy components on the structured superhydrophobic surface exhibited a very low surface energy of similar to 4.6 mN/m at room temperature and ultrahigh water contact angle >175 degrees. The interaction between water droplets on the nonwetting surface was comprehended and correlated to the temperature-dependent surface energy properties. The surface energy and wettability of the structured pseudoboehmite superhydrophobic surface exhibited an inverse behavior as a function of temperature. Interestingly, the superhydrophobic surface exhibited "Leidenfrost effect" below the boiling point of water (67 degrees C), which is further correlated with the intermolecular forces, interfacial water molecules and surface-terminated groups. These high-temperature wetting transition studies could be potentially valuable for solid-liquid systems working at nonambient temperatures, and also this approach can pave new pathways for better understanding of the solid/liquid interfacial interactions on nanoengineered superhydrophobic surfaces.