Perovskite-type oxides with a chemical formula of
ABO
3 exhibit various functional properties. Among them, lithium ion-conducting oxides with
A-site deficient perovskite-type structure such as La
2/3-xLi
3xTiO
3 show fast lithium ion conductivity of 10
-5 to 10
-3 S/cm at room temperature. The high conductivity is attributable to the percolation-controlled diffusion of lithium ions in the vicinity of
A-site via vacancy. In this report, recent research on perovskite-type lithium ion-conducting oxides are reviewed in terms of crystal structure including microstructure, and chemical bond. The relationship among structure, chemical bond, especially second-order Jahn-Teller effect attributable to the covalent bond between
B ion with d
0 electronic configuration and O ion, and lithium-ion diffusion are discussed.
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