The composite materials of LiFePO4 powder coated with polyacenic semiconductor materials (PAS) were successful prepared. Effects of the preparation conditions, such as precursor material, annealing temperature et al., on the structure and electrochemical properties of LiFePO4 were studied. SEM images and TG thermogravimetric analysis of the obtained carbon coating microspheres suggest that LiFePO4 powder was successfully encased within the carbon gel microspheres. The electrical conductivity of the composite materials could get to 10-2 S•cm-1. It was found that the composite LiFePO4 material exhibits excellent capability with initial discharge capacity more than 210 mAhg–1. The discharge capacity goes up to 340 mAh/g after ten times of cycle.