Li-rich oxide cathodes are drawing increasing attention as next-generation cathode materials for the development of high-energy-density Li-ion batteries due to their strikingly high capacities. However, transition-metal migration, irreversible structural phase transformations, and the irreversible release of oxygen are responsible for rapid capacity and voltage decay. This study reports a Li-rich cation-ordered rock-salt oxide LixV0.4Ti0.4O2(LVTO, x = 0.97/1.2) with space group Fd3¯ m that delivers a high capacity of over 250 mAh g-1and capacity retention up to 89% after 50 cycles. A comprehensive experimental analysis confirms that the capacity can be attributed to the reversible V3+/V5+multielectron cationic redox reactions and a minor contribution from reversible anionic redox reactions. Importantly, LVTO exhibits nearly zero-strain behavior upon (dis)charge cycling cycles, which is associated with reversible V migration from octahedral to tetrahedral sites. Our results demonstrate that Li-rich rock-salt oxide LVTO could be a promising cobalt-free cathode material for Li-ion batteries.