Abstract: LiFePO4 was successfully synthesized as a product via one-step solid-state reaction during which the raw materials were embedded in graphite powder instead of the protective atmosphere when heated at high-temperature. The structure, morphology and electrochemical properties of the product were investigated by XRD, FTIR, SEM and galvanostatic charge/discharge test. The process of lithiation/delithiation of Li⁺ in LiFePO4 electrode was studied by cyclic voltammetry. The results showed that the pure-phase olivine-type LiFePO4 composed of near spherical particles in sub-micrometered size can be obtained by this improved solid-state method. The LiFePO4 thus prepared has favorable multiplication rate and cycling stability. The initial discharge specific capacity is 148.3 and 131.9mAh·g^-1 if the rate is 0.1 C and 1 C, respectively; and after the charge/discharge action cycles 50 times the capacity holding rate is 96% and 90% if the rate is 1 C and 5 C, respectively. As calculated according to cyclic voltammetry, the apparent Li⁺ diffusion coefficients are 1.64×10^-13 and 1.94×10^-13 cm²·s^-1 at the peaks of corresponding CV curves of anode and cathode, respectively.