The low electronic conductivity and Li ion diffusion ability are two major obstacles to realize its wide application for LiFePO4 materials. The material with hierarchical conductive structure and lower antisite defects concentration can effectively enhance the electronic conductivity and Li ion diffusion ability. We firstly report here a modified solvothemal process for the fabrication of hierarchical conductive C/LiFePO4/CNTs composite with less antisite defects. It is found that the modified solvothemal process is facilitated to decrease FeLi antisite defects and enhance the electronic continuity between LFP and CNTs. In favor of its unique properties, the C/LFP/CNTs composites can deliver superior rate capability and cycling stability. Remarkably, even at a high rate of 20C (3400mAg−1), a high initial discharge capacity of 91.6mAhg−1 and good cycle retention of 95% with almost 100% coulombic efficiency are still obtained after 100 cycles.