In this paper, Na2Li2Ti6O14 anode materials are synthesized by solid-state reaction and sol–gel method, respectively. Sol–gel formed Na2Li2Ti6O14 shows smaller particle size (0.05–0.1μm) than that (0.2–0.4μm) of samples prepared by solid-state reaction. Electrochemical results show that all the four samples have similar reduction peak at 1.20V and oxidation peak at 1.35V with average working potential of 1.28V. Among all the as-obtained compounds, Na2Li2Ti6O14 synthesized by sol–gel method at 700°C shows the highest initial charge specific capacity of 106.6mAhg−1. After 40cycles, the reversible charge capacity can be maintained at 114.7mAhg−1. Moreover, this sample shows excellent rate properties with a high reversible charge capacity of 110mAhg−1 at 160mAg−1. The improved electrochemical performance is attributed to the proper particle size, high specific surface area and decreased electrochemical resistances. Therefore, Na2Li2Ti6O14 prepared from sol to gel technique will be a promising high-power anode material for rechargeable lithium-ion batteries.