Mn-doped LiNiVO4 and LiCoVO4 were obtained by aqueous method under ambient pressure in the whole 0 ≤ x ≤ 0.4 (LiMn x Ni1−x VO4) and 0 ≤ y ≤ 0.3 (LiMn y Co1−y VO4) region. The lattice constants and reversible capacities of the Mn-doped inverse spinel increased by increasing the Mn doping level. In particular, the reversible capacity of the obtained LiMn0.3Co0.7VO4 is around about 100 mAh g−1, which is the largest reported capacity of inverse spinel cathode materials. It suggests that the bottleneck for lithium diffusion in the inverse spinel structure was enlarged by relatively larger Mn substitutional doping to Co or Ni. The ex-situ XRD measurement for charged or discharged inverse spinel pellets revealed a reversible expansion and contraction on cycle due to the structural strength and flexibility.