Despite considerable research interest due to omnipresent and practical importance of interfacial phenomena (e.g., wetting and dewetting) on nanotextured surfaces in the academic and industrial fields, direct visualization of the behavior and shapes of liquid-vapor interfaces between nanoscale structures remains an arduous task because of the resolution limitations of visualization techniques. In this study, we succeeded in a first-hand visualization of the behavior and shapes of the liquid-vapor interfaces of a water droplet between nanometer-scale pillar during evaporation by introducing a synchrotron X-ray imaging technique with spatially high resolution (40 nm/a pixel). On the basis of the visualization data, we intensively analyzed and discussed the spreading and evaporation phenomena of a liquid droplet on hydrophilic nanotextured surfaces.