LiFePO4 can be used as a positive electrode material for lithium-ion batteries by making composite with electrical conductive carbonaceous materials. In this study, LiFePO4/C (carbon) composite was prepared by a soft chemistry route, in which sucrose was used as a carbon source of a low price. We tried to optimize a Li/(LiFePO4/C) cell performance through changing synthetic conditions and discussed the factors affecting the electrochemical performances of the cell, such as the amount of the carbon source, synthetic temperature, gas flow rate of pyrolysis and the formation of secondary phases. It was found that the connection of the residual carbon and Fe2P to LiFePO4 particles and the amount of these two phases were important factors. In our experimental conditions, LiFePO4/C including 9.72wt.% of residual carbon, prepared at 800°C for 12h showed the highest reversible capacity and the best C rate performance among the synthesized materials; 130mAhg−1 at 10C rate and 50°C.