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Nanostructured strontium titanate (SrTiO3) thin films are studied by high temperature photoelectron spectroscopy and thermal gravimetric analysis. The results indicate that ion migration and redistribution as well as transformation between lattice oxygen and gas phase oxygen take place near the grain boundaries during thermodynamic equilibrium process, which lead to obvious variation of the surface composition with temperature. The lattice oxygen ions migrate from bulk to grain surface with temperature rising up; meanwhile Ti ions also migrate to grain surface and combine with oxygen ions forming Ti-O complex. An opposite process takes place during temperature falling down, but the latter process is much slower than the former one. A primary model is proposed to explain this phenomenon.