In this paper, a series of Na2−2xBaxLi2Ti6O14 (x=0, 0.25, 0.5, 0.75, 1) samples are prepared simply by a solid state reaction method, and among them, NaBa0.5Li2Ti6O14 (x=0.5) exhibits the smallest particle size and best electrochemical properties. According to the electrochemical results, the initial charge specific capacity of NaBa0.5Li2Ti6O14 (x=0.5) reaches 109.6mAhg−1 at the current density of 50mAg−1, which is much higher than other samples. The reversible capacity can still be held at 108.6mAhg−1 after 50cycles. In addition, NaBa0.5Li2Ti6O14 (x=0.5) also displays outstanding rate property with high charge specific capacities of 128.8, 117.7, 110, 100.2, 98.1mAhg−1 at 100, 200, 300, 400 and 500mAg−1, respectively. Our results suggest that the smaller particle size, decreased electrochemical resistance and improved ionic conductivity of Na2Li2Ti6O14 after Ba doping are main contributing factors in enhancing the lithium storage capability, and among them, NaBa0.5Li2Ti6O14 (x=0.5) is a potential anode material for rechargeable lithium-ion batteries.