High-purity SrTiO3 bicrystal sample (the angle between two [001] directions is 24°) was used in the present experiment to develop a thermal grain boundary groove along the bicrystal grain boundary at different temperatures (1150–1400 °C) and times (15–6720 min) in air. An atomic force microscope (AFM) was used to observe the surface morphological change in the annealed bicrystal sample in order to measure the width W and depth h of the developed grain boundary groove. It was found that the log W–log t (at 1150–1400 °C) and the log h°log t (at 1400 °C) relationships are approximately linear, having slopes of approximately 1/4. Using Mullins' formulas, the surface diffusion coefficients of SrTiO3 at different temperatures were calculated. Finally, the surface diffusion coefficient determined in the present experiment appears to correspond to the titanium atom, which has the lowest diffusivity in SrTiO3.