Carbon free LiFe1−xMnxPO4 (x = 0, 0.05, 0.1, 0.2, 0.4) cathode materials were prepared by a direct-hydrothermal process at 170 °C for 10 h. The structural and electrochemical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), charge–discharge experiments, cyclic voltammetry (CV) and alternating current (AC) impedance spectroscopy. The electrochemical performance of LiFePO4 prepared in this manner showed to be positively affected by Mn2+-substitution. Among the Mn2+-substitution samples, the LiFe0.9Mn0.1PO4 exhibited an initial discharge capacity of 141.4 mA h g−1 at 0.1 C, and the capacity fading is only 2.7% after 50 cycles.