Novel electrode materials with nominal compositions of (1− x)LiVO2·xLi2TiO3 (0≤ x ≤0.6) were synthesized by carbothermal reduction reaction. All the materials were identified to have a layered structure and can be considered as a solid solution related to LiVO2–Li2TiO3 system, in which Li layers was alternately stacked with the layers made of mixture of Li, V, and Ti in a ccp array of oxygen. The redox reaction associated with vanadium ions was not reversible in LiVO2; however, introduction of the redox couple into Li2TiO3 made it much more reversible. A reversible capacity of about 120mAhg−1 remained after 90 cycles for the samples with x =0.5 and 0.6, when they were cycled in the voltage range of 1.0–4.8V.