It is essential to improve the electron and lithium ion conductivities of Lithium iron(II) phosphate (LiFePO4) used as a cathode material for lithium-ion batteries. In the work, we designed and fabricated a series of composites of LiFePO4 modified cooperatively with chemically reduced graphene oxide (RGO) and polyaniline. It was demonstrated that the composites have a three dimensional network structures in which the CRGO and the polyaniline were intertwined and coated uniformly on the surface of LiFePO4. Comparably, as cathode for lithium-ion batteries, the as-prepared composites showed better electrochemical performances than the bare LiFePO4 and the LiFePO4 modified simply with CRGO or polyaniline alone. The elaboration of the underneath mechanism on the pronounced electrochemical properties of the composites was also attempted and discussed.