The topmost atoms of TiO2 - terminated SrTiO3(001) annealed at temperatures between room temperature and 800°C in ultra high vacuum (UHV), have been studied by means of in-situ coaxial impact collision ion scattering spectroscopy (CAICISS). Both time-of-flight spectra at the incident angle of 45.0°C along [ 100] azimuth and of 35.3°C along  azimuth revealed Ti and weak O peaks and no Sr peak at 150°C, which means that the topmost layer at 150°C is terminated by TiCh-plane, completely. On the other hand, as increasing the substrate temperature, Sr peak began to appear above 400°C. This Sr peak intensity from both directions was drastically increased with elevating the substrate temperature. This indicates that the topmost O and Ti atoms desorb from the surface at the higher substrate temperature. The ratio Sr/Ti corresponds to the amount of the topmost oxygen or titanium vacancies due to the desorption. It was found that 40 % of the topmost oxygen atoms and 32% of the topmost titanium atoms desorb from TiO2-terminated SrTiO3(001) surface at 800°C. The activation energies for oxygen and titanium desorption were 0.28eV and 0.40eV, respectively.