To modify oxide structure and introduce a thin conductive film on Li4Ti5O12, thermal nitridation was adopted for the first time. NH3 decomposes surface Li4Ti5O12 to conductive TiN at high temperature, and surprisingly, it also modifies the surface structure in a way to accommodate the single phase Li insertion and extraction. The electrochemically induced Li4+delta Ti5O12 with a TiN coating layer shows great electrochemical properties at high current densities.