Considering the charming merits and natural defects of Li4Ti5O12 (LTO), we build a hierarchical LTO/C composite through a rational hydrothermal route by utilizing the low-cost glucose as carbon source. The obtained composite consists of some grain-like secondary particles (10–15nm) pasted on the relatively bulk LTO sheets (50–100nm). Due to the introduction of carbon, the composite has the smaller particle size, lower polarization and superior electrical conductivity. Besides, the as-prepared sample exhibits good cycling stability and outstanding rate performance. It delivers the discharge capacity of 174.1mAhg−1 at 1C and left 131.7mAhg−1 even at 50C, which is apparently superior than pristine LTO. Furthermore, the discharge capacity maintains 93.4% after 500 cycles at 1C and 80.5% after 1000 cycles at 50C. Even after 3000 ultralong cycles at 5C, the value still retains 74.2% which is much higher than that of pure LTO (38.4%). The ideal proportion of carbon modified in LTO is also explored. The LTO/C-3.74wt% composite is demonstrated to possess optimal electrochemical performance.