Recently, in situ transmission electron microscopy (TEM) has provided a route to analyze structural characterization and chemical evolution with its powerful and unique applications. In this paper, we disclose the detailed phenomenon of sublimation on the atomic scale. In2Se3/In2O3 nanowires were synthesized via the vapor-liquid-solid mechanism and studied in an ultra-high-vacuum (UHV) TEM at high temperature in real time. During in situ observation of the sublimation process of the nanowires, the evolution and reconstruction of the exposed In2Se3 surface progressed in different manners with time. The surface structure was decomposed by mass-desorption and stepwise-migration processes, which are also energetically favored processes in the ab initio calculation. This study developed a new concept and will be essential in the development of atomic kinetics.