Lithium-ion conductivity is one of the critical factors in improving the rate capability of LiFePO4 in lithium- ion batteries. The one-dimensional diffusion pathway of lithium ions slows the charging/discharging rates in the olivine structure of LiFePO4. Herein, ultrathin LiFePO4 nanosheets were synthesized using surface-passivating ligands to address the rate capability issue. The thickness direction of the nanosheets is the [010] direction in which the lithium ions are inserted or extracted during cycling. The structural and morphological characterizations were performed via transmission electron microscopy and X-ray diffraction. A thickness of 7.5 nm was obtained from the atomic force microscopy height profiles, which is in the scale of twelve unit cells of LiFePO4. Electrochemical performance test results revealed that the Li-ion batteries had superior rate capability during the charging/discharging process.