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Spherical LiFePO4/C composite was prepared via a low-temperature solvothermal reaction followed by high-temperature treatment. The as-prepared sample was characterized by XRD, SEM, FTIR, cyclic voltammetry(CV) and galvanostatic charge-discharge tests. It was confirmed that the spherical LiFePO4/C were composed of crystalline LiFePO4 with a size of c.a.10 μm. As-prepared micrometer-sized spherical LiFePO4 particles were successful in overcoming the major limitation of volumetric energy density and reached a high tap density of 1.4g.cm-3. The charge-discharge tests showed that the as-fabricated spherical LiFePO4/C cathode in lithium-ion cells demonstrated high reversible capacity (154 mAh g.1 at 0.1C, 135.2 mAh g.1 at 0.2C,115 mAh g1 at 1C) and good cycle stability (columbic efficiency 100％ after 50 cycles). Compared with the nano-LiFePO4 positive electrode material, this spherical and nanoporous materials resulted in a similarly high rate capability plus a higher volumetric energy density. So, as-prepared LiFePO4/C powder with high tap density makes an attractive positive electrode candidate for lithium-ion batteries designed for high energy density.