Li2Na2Ti6O14 and its Ti-site substitution Li2Na2Ti5.9M0.1O14 (M = Al, Zr, V) are prepared by a solid-state reaction method and used as anode materials for lithium-ion batteries. It is found that metal doping can effectively enhance the electronic conductivity and ionic diffusion coefficient of Li2Na2Ti6O14. Especially for Li2Na2Ti5.9Al0.1O14, it reveals the highest electronic conductivity (1.02 × 10−9 S cm−1) and lithium ion diffusion coefficient (8.38 × 10−15 cm2 s−1) among all the samples. As a result, Li2Na2Ti5.9Al0.1O14 reveals the best electrochemical performance. It can deliver a charge specific capacity of 270.3 mAh g−1 at 50 mA g−1. Even cycled at 1000 mA g−1, it still can present a charge capacity of 180.7 mAh g−1. All these enhanced lithium storage capabilities of Li2Na2Ti5.9Al0.1O14 should be attributed to the increased electronic/ionic conductivities and the decreased charge transfer resistance induced by Al doping. Besides, in-situ X-ray diffraction observation also confirms that the structural change of Li2Na2Ti5.9Al0.1O14 is highly reversible process for lithium storage.