A rigid crystal lattice, where cations occupy specific positions in the lattice, is generally regarded a critical requirement to enable Li+ diffusion in the bulk of conventional cathode materials, while disorder is generally considered as detrimental. Herein, we demonstrate that facile and reversible insertion and extraction of Li+ is possible with LiVO2, a new cation‐disordered rock salt compound (space group:Fm3 ̅m), which is, to the best of our knowledge, described for the first time. This new polymorph of LiVO2 is synthesized by mechanical alloying. Rietveld refinements of the X ray diffractions patterns and SAED (selected area electron diffraction) patterns attested the formation of the disordered LiVO2 rock salt phase. Galvanostatic cycling experiments were employed to characterize the electrochemical performance of the material, demonstrating that reversible cycling over 100 cycles with a discharge capacity around 100 mAh g‐1 is possible.