The energy crisis and energy security leads a great attention to Li-ion batteries (LIB) as the excellent power candidates. We successfully synthesized LiMnPO4·Li3V2(PO4)3/C composite cathode material with high capacity and excellent cycling performance from prickly MnV2O6·2H2O precursor, following chemical reduction and lithiation with double carbon sources. The LiMnPO4·Li3V2(PO4)3/C sample has a special multicore-shell structure, whose inner stuffing are LiMnPO4 and Li3V2(PO4)3 in the range of 5-25nm. The initial discharge capacity of LiMnPO4·Li3V2(PO4)3/C composite delivers 221.4mAhg−1, 202.3mAhg−1 and 152.9mAhg−1 at the rate of 0.1C, 1C and 5C in the range of 1.5-4.5V, and retains 99.5%, 99.1% and 94.3% of its initial discharge capacity after 50 cycles, respectively.