In this study, the B-doped carbon coating has been applied to enhance the lithium-storage performance of Li4Ti5O12 anode material for Li-ion batteries. The designed B-doped carbon improved Li4Ti5O12 composite (abbreviated as Li4Ti5O12@C-B) is successfully synthesized using a sol-gel approach followed by a microwave heating route. The XRD and HRTEM results demonstrate that the well-crystallized Li4Ti5O12 particles are uniformly coated with the B-doped carbon layer with a thickness of about several nanometers. The existence of boron doping in the carbon layer is also confirmed by XPS and EDX mapping. Compared with the undoped Li4Ti5O12@C, the Li4Ti5O12@C-B anode shows superior electrochemical performances such as higher reversible capacity and better cycling stability. The enhanced lithium-storage property can be attributed to the doped boron element which could bring many amazing improvements on the carbon coating. Therefore, this novel strategy of B-doped carbon coating can be widely used to improve the electronic conductivity of other electrode materials for electrochemical energy storage.