The preparation and characterization of Pb1-x Ba x Li2Ti6O14 (x = 0, 1/4, 1/2, 3/4, 1) as anode materials for lithium ion batteries are investigated in this research. The structure, morphology and electrochemical properties are compared with each other by changing the Pb/Ba atomic ratio in Pb1-x Ba x Li2Ti6O14. It can be observed that each sample shows the same orthorhombic structure with Cmca space group. Moreover, it can also be found that the working potential, conductivity, cycling and rate performances of as-received samples gradually change along with the evolution of x in Pb1-x Ba x Li2Ti6O14 (x = 0, 1/4, 1/2, 3/4, 1). Electrochemical evaluation shows that the operating potential of the as-received sample gradually decreases with increasing x value in Pb1-x Ba x Li2Ti6O14 and its initial charge capacity increases reversely. Moreover, different Pb/Ba atomic ratio also brings different cycling stability for Pb1-x Ba x Li2Ti6O14. Especially for Pb3/4Ba1/4Li2Ti6O14, it presents better electrochemical properties than other samples. After 120 cycles, the reversible capacity of Pb3/4Ba1/4Li2Ti6O14 is maintained at 129.7 mAh g−1 with capacity retention of 88.3%. In addition, its electrochemical reversibility is also demonstrated by in-situ X-ray investigation.