An effective way to improve the conductivity of LiFePO4 is by the introduction of conductive carbon. The carbon structure is an important component needed to obtain optimal electrochemical performance. In the present work, an Olivine-type LiFePO4 powder has been synthesized from amorphous Fe-3(PO4)(2) and Li3PO4 center dot 1/2H(2)O by solid-state methods. For purposes of comparison, the phenol-formaldehyde resin was added as a carbon precursor to convert the polyacenic semiconductor (PAS). This compound is a form of amorphous carbon with decent carbon structures formed after low heat treatments. The electric conductivity of the synthesized LiFePO4/PAS composite has been raised by seven orders of magnitude. The resultant electrochemical performance was tested and lower polarization, higher rate capacity, and better cycling ability were obtained.