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The oxide perovskite family holds great promise for diverse applications on account of their unique chemical and physical properties. However, owing to the inadequate Li + -storage sites, the insertion-type perovskite anodes for lithium-ion batteries (LIBs) are limited. A-site deficient perovskites with rich intrinsic vacancies and ion transport channels are believed to be the desirable hosts of superior Li + storage. Herein, the perovskite Li 0.1 La 0.3 NbO 3 (LLNO) is designed and demonstrated as the remarkable anode for LIBs with a high specific capacity, a safe operating voltage, an excellent rate performance, and a long cycling life. More importantly, the outstanding cycling stability of LLNO is originated from its low strain characteristic with a maximum volume change of only 1.17%. The exceptional rate performance can be explained by the unconventional Li + transport pathways with external → grain boundaries → lattice deficiencies. These results not only reveal that A-site deficient perovskite LLNO is a promising anode for LIBs but also provide fundamental insights into the Li + ions transport mechanism, facilitating the development of high-performance perovskite anodes.

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