A microwave-assisted hydrothermal approach combined with carbothermal reduction has been developed to synthesize monodisperse porous LiFePO4/C microspheres, which possess the diameter range of 1.0–1.5 μm, high tap density of ∼1.3 g cm−3, and mesoporous characteristic with Brunauer–Emmett–Teller (BET) surface area of 30.6 m2 g−1. The obtained microspheres show meatball-like morphology aggregated by the carbon-coated LiFePO4 nanoparticles. The electrochemical impedance spectra (EIS) results indicate that carbon coating can effectively enhance both of the electronic and ionic conductivities for LiFePO4/C microspheres. The Li-ion diffusion coefficient of the LiFePO4/C microspheres calculated from the cyclic voltammetry (CV) curves is ∼6.25 × 10−9 cm2 s−1. The electrochemical performance can achieve about 100 and 90 mAh g−1 at 5C and 10C charge/discharge rates, respectively. As cathode material, the as-prepared LiFePO4/C microspheres show excellent rate capability and cycle stability, promising for high power lithium-ion batteries.