Three-dimensional porous self-assembled LiFePO4/graphene (LFP/G) composite was successfully fabricated using a facile template-free sol–gel approach. Graphene nanosheets were incorporated into the porous hierarchical network homogenously, which greatly enhances the electrical conductivity and efficient use of the LiFePO4 (LFP), leading to an outstanding electrochemical performance of the hybrid cathodes. The obtained LFP/G composite has a reversible capacity of 146mAhg−1 at 17mAg−1 after 100 cycles, which is more than 1.4 times higher than that of porous LFP (104mAhg−1). Moreover, the porous LFP/G composite also exhibits a desirable tolerance to varied charge/discharge current densities.