jats:titleAbstract</jats:title> jats:pThe strontium titanate (SrTiOjats:sub3</jats:sub>) single crystals with different orientations of (100), (110) and (111) were investigated using thermally stimulated depolarization current (TSDC) measurements, which has been proved to be an effective strategy to fundamentally study the relationship between relaxation phenomena and defect chemistry in dielectrics. The origins of different relaxations in SrTiOjats:sub3</jats:sub> crystals were identified and the activation energy of oxygen vacancies was estimated from TSDC measurements. It was further found that oxygen-treated SrTiOjats:sub3</jats:sub> crystals exhibit different relaxation behaviors. Noticeable changes of thermal relaxation associated with oxygen vacancies have taken place in relation to the crystalline anisotropy. The SrTiOjats:sub3</jats:sub> (110) samples display higher concentration and activation energy of oxygen vacancies. First-principles calculations were carried out on SrTiOjats:sub3</jats:sub> (110) crystals to study the effect of oxygen vacancy on different surface microstructure. From the resulting minimum formation energy of 0.63 eV, it demonstrates that the oxygen vacancies tend to form on the TiO-terminated surfaces. Considering the band structure, oxygen vacancies near the surface contribute to the transition of crystal from insulator to metallic characteristic.</jats:p>