Metal doping is an effective way to improve the electrochemical properties of titanates. In this work, Ba-site substituted Ba0.9M0.1Li2Ti6O14 (M=K, Zn, La) are synthesized to fabricate high performance titanate anode for lithium-ion batteries. Electrochemical evaluations reveal that introducing metal doping at Ba-site can result in higher ionic/electronic conductivity. As a result, Ba0.9M0.1Li2Ti6O14 exhibits enhanced lithium storage capability. Especially for Ba0.9La0.1Li2Ti6O14, it shows the best electrochemical performance with a high reversible charge capacity of 151.3mAhg−1 and high capacity retention of 94.21% at a current density of 100mAg−1. For comparison, the pristine BaLi2Ti6O14 only exhibits a reversible charge capacity of 128.5mAhg−1 with the capacity retention of 80.06% after 100 cycles. Further, the lithium storage process is investigated in detail by in-situ structural observation, which reveals a maximum volume expansion of 1.9% for Ba0.9La0.1Li2Ti6O14 during charge-discharge cycle. It shows that Ba0.9La0.1Li2Ti6O14 is a possible material with high structural reversibility for lithium storage.