Submicronic particles of LiFePO4 were synthesized by hydrothermal method at 185 °C assisted by carboxylic acid route. In this work, we used citric acid to control the pH of the final products and studied the influence of synthetic conditions on the physical and electrochemical properties of LiFePO4. Structural characterization includes XRD, SEM, TEM and FTIR experiments. The powder quality was investigated by magnetic measurements. Electrochemical features of C–LiFePO4 in Li cell using 1 mol L−1 LiPF6-EC-DEC electrolyte show an excellent capacity retention of 158 mAh g−1 for material prepared with R(citric acid/Fe) = 7 mol%.