In this work, Na2Li2Ti6O14 and its Li-site substitution Na2Li1.9M0.1Ti6O14 (Mn+ = Na+, Mg2+, Cr3+, Ti4+, V5+) samples are synthesized by a simple solid state reaction route and evaluated as anode materials for lithium-ion batteries. Their crystal structures and ion doping behaviors are described and verified by Rietveld refinement. Electrochemical results exhibit that Na+, Mg2+ and Cr3+ dopings can effectively improve the lithium storage capability of Na2Li2Ti6O14. Especially for Na2Li1.9Cr0.1Ti6O14, it shows the best cycling and rate properties among all the as-prepared samples, with a cycling reversible capacity of 262.2 mAh g−1 at 100 mA g−1 and a rate charge capacity of 233.3 mAh g−1 at 700 mA g−1. The enhanced electrochemical properties are contributed to the reduced particle size, decreased charge transfer resistance and improved ionic diffusion coefficient of Na2Li2Ti6O14 via Cr3+ doping. Furthermore, the zero-strain characteristic should also be responsible for the outstanding lithium storage capability of Na2Li1.9Cr0.1Ti6O14. Besides, in-situ X-ray diffraction also reveals that Na2Li1.9Cr0.1Ti6O14 has high structural stability and reversibility during charge–discharge process. Therefore, Na2Li1.9Cr0.1Ti6O14 may be a probable high performance anode material for lithium-ion batteries.