Ultra‐long‐life (at least 10 000 cycles) lithium‐ion batteries are very effective for stationary energy‐storage applications. However, even "zero‐strain" materials with small unit‐cell‐volume changes of <1% cannot last for ultra‐long cycles due to gradually accumulated intracrystal strain/stress. Here, Li[Li0.2Cr0.4Ti1.4]O4 is explored as the first absolutely‐zero‐expansion material with unit‐cell‐volume variations of zero during Li+ storage. Its absolutely‐zero‐expansion mechanism is intensively studied, revealing that 16c‐octahedron shrinkage fully offsets 16d‐octahedron expansion through reversible O2− movement. It delivers better cycling stability than, as far as we know, all electrochemical energy‐storage materials previously reported. Its capacity retention at 10 C and 1.0 mg cm−2 after 17 000 cycles reaches 91.5%. When the active‐material loading significantly increases to 6.4 mg cm−2, its capacity retention at 5 C after 500 cycles reaches 95.7%. At an elevated temperature of 45 °C, it not only keeps excellent cycling stability but also exhibits significantly enhanced rate capability. Therefore, Li[Li0.2Cr0.4Ti1.4]O4 is especially suitable for stationary energy storage. [ABSTRACT FROM AUTHOR]