Li2FeSiO4/C cathode materials have been prepared using the conventional solid-state method by varying the sintering temperature (650 °C, 700 °C and 750 °C), and the structure and electrochemical performance of Li2FeSiO4/C materials are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, respectively. The results show that Li2FeSiO4 nano-crystals with a diameter of about 6–8 nm are inbedded in the amorphous carbon, and the Li2FeSiO4/C material obtained at 700 °C exhibits an initial discharge capacity of 195 mA h g−1 at 1/16 C in the potential range of 1.5–4.8 V. The excellent electrochemical performance of Li2FeSiO4/C attributes to the improvement of conductivity and reduction of impurity by the optimization of the sintering temperature.