Li1+xV1−xO2 (0 ≤ x ≤ 0.1) compounds were studied as the anode materials for a lithium-ion battery. The crystal and electronic structures of the prepared materials were correlated with electrical conductivities and electrochemical properties. The electrochemical behaviors were significantly dependent on the composition of Li1+xV1−xO2, and these were resulted from the perturbation of the local electronic structure arising from the increase in lithium contents in Li1+xV1−xO2 rather than from the slight distortion in the crystal structure. The electrical conductivities of Li1+xV1−xO2 increased with the increase in lithium contents in the compounds. Li1.1V0.9O2 and Li1.075V0.925O2 samples exhibit the first discharge capacities of 250 and 241 mAh g−1 at 0.2 C-rate, respectively.