© 2020 Science China Press Oxygen vacancy is one of the pivotal factors for tuning/creating various oxide properties. Understanding the behavior of oxygen vacancies is of paramount importance. In this study, we identify a metastable oxygen vacancy ordering state other than the well-known Magnéli phases in TiO2 crystals from both experimental and theoretical studies. The oxygen vacancy ordering is found to be a zigzag chain along the [0 0 1] direction in the (1 1 0) plane occurring in a wide temperature range of 200–500 °C. This metastable ordering state leads to a first-order phase transition accompanied by significant enhancement of dielectric permittivity and a memristive effect featuring a low driving electric field. Our results can improve oxide properties by engineering oxygen vacancies.