Olivine-structured LiFePO4/C composites with high rate-performance were synthesized via an industrial spray-drying technique using a low cost Fe3O4 as iron source. The as-obtained LiFePO4/C exhibits a unique bowl-like morphology with a particle size of 2–5 μm in diameter. A continuous uniform carbon coating layer on the surface of LiFePO4/C cathodes promotes fast electron transport, whilst it guarantees the favorable electrochemical reaction. Especially the formation of porous structure leads to an average pore volume of 0.127 cm3 g−1 and a high specific surface area of 34.46 m2 g−1, which is conducive to facilitating the penetration of electrolyte and providing the more contact area of electrolyte with LiFePO4/C. As a result, the as-prepared LiFePO4/C cathode material delivers an outstanding discharge capacity of 102.1 mAh g−1, 94.2% of the initial capacity (108.3 mAh g−1), after 1000 cycles at 10 C. Even at an ultrahigh current rate of 50 C, it still shows an initial discharge capacity of 58 mAh g−1.