Nitrogen-doped 3D flower-like carbon materials (NFCs) have been fabricated using a simple and effective strategy, namely, the hierarchical assembly of polyimide (PI) and subsequent thermal treatment. The effect of pyrolysis temperature on the structural evolution process of PI is also investigated systematically. When evaluated as anode materials for lithium ion batteries (LIBs), the as-obtained NFCs, especially NFCs-550, exhibit good electrochemical performance, including a high reversible capacity (1488.1 mAh g(-1) at 0.05 A g(-1)), excellent rate performance (287.6 mAh g(-1) at 2 A g(-1)), and good cycling stability (645 mAh g(-1) with 96% retention after 300 cycles at 0.1 A g(-1)). The good electrochemical performance is attributed to the synergistic effect between 3D flower-like nanostructure and high nitrogen content. This approach may provide some inspiration to construct a series of heteroatom doped and hierarchical structured carbon materials using polymers for LIBs. (C) 2017 Elsevier B.V. All rights reserved.