The energy crisis and energy security leads a great attention to Li-ion batteries (LIB) as the excellent power candidates. We successfully synthesized LiMnPO4 center dot Li3V2(PO4)(3)/C composite cathode material with high capacity and excellent cycling performance from prickly MnV2O6 center dot 2H2O precursor, following chemical reduction and lithiation with double carbon sources. The LiMnPO4 center dot 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 center dot Li3V2(PO4)(3)/C composite delivers 221.4 mAh g(-1), 202.3 mAh g(-1) and 152.9 mAh g(-1) at the rate of 0.1C, 1C and 5C in the range of 1.5-4.5 V, and retains 99.5%, 99.1% and 94.3% of its initial discharge capacity after 50 cycles, respectively. (C) 2015 Elsevier Ltd. All rights reserved.