A series of Li2BaTi6O14 samples are synthesized by a traditional solid-state method by calcining at different temperatures from 800 to 1000 °C. Structural analysis and electrochemical evaluation suggest that the optimum calcining temperature for Li2BaTi6O14 is 950 °C. The Li2BaTi6O14 calcined at 950 °C exhibits a high purity phase with an excellent reversible capacity of 145.7 mAh g−1 for the first cycle at a current density of 50 mA g−1. After 50 cycles, the reversible capacity can be maintained at 137.7 mAh g−1, with the capacity retention of 94.51%. Moreover, this sample also shows outstanding rate property with a high reversible capacity of 118 mAh g−1 at 300 mA g−1. The excellent electrochemical performance is attributed to the stable lithium storage host structure, decreased electrochemical resistance and improved lithium-ion diffusion coefficient. In-situ and ex-situ structure analysis shows that the electrochemical reaction of Li2BaTi6O14 with Li is a highly reversible lithiation–delithiation process. Therefore, Li2BaTi6O14 may be a promising alternative anode material for lithium-ion batteries.