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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 …