Mesoporous spherical Li4Ti5O12/TiO2 composites have been synthesized by a facile aerosol spraying hydrolysis method following calcine at 600°C for 8h. The as-obtained samples were characterized by XRD, SEM, TEM, BET surface area, and XPS. The mesoporous spherical Li4Ti5O12/TiO2 exhibits superior electrochemical performance as an anode material for lithium-ion batteries than both the simple Li4Ti5O12 and non-porous Li4Ti5O12/TiO2. The discharge specific capacity of the mesoporous spherical Li4Ti5O12/TiO2 composite is 161, 143, and 111mAh/g at 1C, 5C and 20C, respectively, and retains 93.04% (145.27mAh/g) capacity after 120 cycles at 2C. Therefore, the as-obtained mesoporous spherical dual-phase Li4Ti5O12/TiO2 composite is potential to be applied as an efficient anode material for Li ion batteries.