Abstract Oxygen vacancies in oxide materials, although has been demonstrated to be beneficial for many applications, are hard to be generated and manipulated as desired, particularly for bulk materials with large size and limited surface area. Here, by simply coupling the thermal activation with simultaneously applied electric field, we efficiently generate ordered oxygen vacancies within bulk crystals of ternary SrAl2O4, binary TiO2 and other common oxide materials, which give rise to superior functionalities. We expect that this approach offers a general and practical way for vacancy engineering of oxide materials and holds great promise for their applications.