Spectroscopic ellipsometric (SE) measurements of GaAs (100) were carried out in an ultrahigh vacuum (UHV) chamber, without arsenic overpressure, at temperatures ranging from room temperature (RT) to ∼610°C. Surface changes induced at elevated temperatures were monitored by in-situ spectroscopic ellipsometry. The SE data clearly displayed in real time the process of desorption of the GaAs-surface-oxide overlayer at ∼580°C. In addition, changes in the near-surface region were observed before and after the oxide desorption. The near-subsurface region (top 50–100 Å) became less optically dense after being heated to 540°C or higher. For comparison, a pre-arsenic-capped molecular-beam-epitaxy (MBE)-grown GaAs surface was also studied. After the arsenic cap was evaporated off at ∼350°C, this surface remained smooth and clean as it was heated to higher temperatures.