Anchor Practically applicable approach for the fabrication of ABO3 perovskites with high rates of ionic transport is developed. The ionic transport in perovskites with transition metals at B – site is considered in terms of the theory of coordination compounds. It is shown that the structure of these materials is sensitive to the values of the effective charge of the ions of transition metals (Z * ) and to the electronegativity (χ) of the surrounding cations. The magnitudes of Z * and χ can be varied by choosing the appropriate elements at sites A and B to induce a distortion of the short range order. This leads to reduction of potential barriers for formation and migration of structural defects including oxygen vacancies. In typical perovskites a correlation between the rates of the ionic transport and the estimated values of Z * and χ is found.