LiFe2/3Mn1/3PO4/C composite was prepared by the rheological phase reaction using LiH2PO4, Li2CO3, FePO4, Mn(Ac)2·4H2O and ascorbic acid as starting materials. The crystal structure and morphology of as-synthesized sample were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The analysis of XRD results showed that the obtained sample was single-phase with orthorhombic olivine-type structure (Pnma space group). SEM micrographs revealed that the sample was aggregates, with an irregular morphology. The initial discharge capacity was 166.9, 149.1, 139.6, 112.8, 82.93 mAh g??1 at the rate of 0.1, 0.5, 1, 2, and 10 C, respectively. And when the rate was 0.1, 0.5, 1, 2, and 10 C, the capacity retention was 92.2%, 90%, 92.9%, 97.6%, 91.5% after 50, 100, 200, 200, 500 cycles, respectively.