MLi2Ti6O14 (M = Sr, Ba, 2Na) titanates have been investigated as lithium insertion materials for lithium-ion batteries. A comparative study has been undertaken based on the structure, morphology, and electrochemical properties of the titanate materials, which were prepared by sol-gel synthesis. Their lithium insertion behavior was analyzed by crystallographic considerations. While Na2Li2Ti6O14 can reversibly host two Li+ ions, SrLi2Ti6O14 and BaLi2Ti6O14 can reversibly insert almost four lithium ions per unit formula. Among the three materials, SrLi2Ti6O14 showed superior capacity and rate capability. It was concluded that this class of materials could be of practical use in high-power lithium batteries for transportation applications.