LiFePO4 in situ coated with hierarchical porous nitrogen-doped graphene-like membrane (HPNGM) composite derived from a electrospun polymer membrane (EPM) precursor has been achieved for the first time. The N-doped graphene-like membrane which is in situ coating on LiFePO4 can provide a highly conductive layer, and the hierarchical porous structure facilitates Li+ transfer. The composite exhibits a high reversible capacity (171 mAh g−1 at 0.1 C), excellent high-rate capability and cycling stability. In addition to construct the traditional structure of nanofiber or nanowire, the EPM can also form graphene-like structure after annealing, which is a new application in constructing sheet structure by electrospinning.