Well-defined Li4Ti5O12 nanosheets terminated with rutile-TiO2 at the edges were synthesized by a facile solution-based method and revealed directly at atomic resolution by an advanced spherical aberration imaging technique. The rutile-TiO2 terminated Li4Ti5O12 nanosheets show much improved rate capability and specific capacity compared with pure Li4Ti5O12 nanosheets when used as anode materials for lithium ion batteries. The results here give clear evidence of the utility of rutile-TiO2 as a carbon-free coating layer to improve the kinetics of Li4Ti5O12 toward fast lithium insertion/extraction. The carbon-free nanocoating of rutile-TiO2 is highly effective in improving the electrochemical properties of Li4Ti5O12, promising advanced batteries with high volumetric energy density, high surface stability, and long cycle life compared with the commonly used carbon nanocoating in electrode materials.