A series of mesoporous LiFePO4/C microspheres have been successfully synthesized via a hydrothermal process using citric acid as chelating agent and reductant. The growth evolution process of the precursor is systematically investigated based on the time-dependent experiments. Pure mesoporous LiFePO4 microspheres are obtained with a diameter of ∼2μm, which are composed of numerous compact nanoparticles (∼200nm). These microspheric LiFePO4 shows high tap density (1.35gcm−3) and large Brunauer–Emmett–Teller (BET) surface area (20.992m2 g−1), which favor the electrochemical properties. The initial discharge capacity of LiFePO4/C microspheres is 163.8mAhg−1 at 0.1C rate, corresponding to 96.4% of the theoretical capacity of LiFePO4 (170mAhg−1). The material also shows excellent high rate capability (120.3mAhg−1, 10C), and cycling stability (a capacity retention of 98.1% at 0.5C rate after 200 cycles).