LiFePO4 electrode material with large specific surface area and porous structure can achieve high energy and power capabilities, but current synthesis method is relatively complicated. Here, we report a facile synthesis of porous–LiFePO4/C (porous–LFP/C) nanocomposites, which require no templates or surfactants. The synthesized porous–LFP/C material possesses outstanding morphology with nano-sized, spherical particles, a desirable core–shell structure with uniform carbon film on the surface of LiFePO4 and with a specific surface area of 29.9 m2 g−1. The as-obtained porous–LFP/C nanocomposites show excellent rate capability and cycling stability. It delivers a discharge capacity of 143 and 126 mAh g−1 at 5C and 10C rates, respectively, and exhibits desirable capacity retention after 500 cycles. Remarkably, it performed well even at 30C (83 mAh g−1) with the 91% of initial capacity after 1000 cycles.