Li2Ti3-xVxO7 and Li4Ti5-xVxO12 (x=0-0.1) are successfully fabricated using the conventional solid-state reaction technique. The battery performance of the cells showed that the highest capacity of Li2Ti3-xVxO7 was obtained for the sample of x=0.025 which has 153mAh/g and 123mAh/g for 1 and 1000, respectively. In addition to this, the best capacity of the cell of Li4Ti4.5V0.5O12 was found as 202mAh/g for the first cycle and it was decreased to 194mAh/g for 1000 cycles. To understand the capacity fade mechanism, we performed ex situ structural experiments and it is found that the unit cell of the crystalline phase is directly affected to battery performance. We concluded that in this study the V-substituted samples have a potential for next-generation battery fabrication since it may cause the increase of the stability of the cells.