A series of SrLi2-xNaxTi6O14 (x = 0.0, 0.05, 0.1, 0.15, 0.2) are synthesized and fabricated as lithium storage anodes for rechargeable batteries. Evaluations of the structure and electrochemical performance suggest that proper Li-site substitution by sodium could effectively improve the lithium-ion diffusion coefficient and reduce the particle size of SrLi2Ti6O14. Among them, it is known that the ideal number of sodium doping content is 0.1 per formula. SrLi1.9Na0.1Ti6O14 reveals better electrochemical performance than bare SrLi2Ti6O14 and other doped samples. It shows an initial charge capacity of 168 mAh g−1 at the current density of 100 mA g−1. After 100 cycles, its reversible capacity is remained at 158 mAh g−1 with excellent capacity retention of 94%. In addition, it also has a good rate performance with the reversible charge capacity of 145 mAh g−1 at 500 mA g−1, reflecting its excellence as lithium host.