A significant increase in the Leidenfrost temperature (LFT) was observed on a micro/nano multiscale textured surface (MTS) compared with a polished surface (PS) and a micro rough surface (MRS). MTS was fabricated by anodic oxidation and has nano-scaled needles with micro roughness. It showed improved surface wetting characteristics (0° contact angle with liquid spreading). On the other hand, MRS was fabricated by mechanical polishing and it only has micro roughness. LFT on MTS and MRS increased by approximately 150 °C and 30 °C, respectively, compared with one for PS. The textures on each surface influenced the water droplet dynamics. The relationship between LFT and the dynamics of water droplet were studied by high-speed photography. The key phenomenon determining LFT was the rebound process of the droplet during a few milliseconds. On MRS and MTS, the rebound phenomenon of the droplet was disturbed by the surface-texture-induced liquid-solid contact even when the surface was initially at a high temperature over 300 °C. The precursor wetting front, observed only on MTS and the capillary wicking phenomenon are likely the responsible mechanisms that significantly increased LFT on MTS.