The Mn(VO3)2 nanosheet was prepared as a precursor to synthesize LiMnPO4·Li3V2(PO4)3/C composite material. The nanograins and nanorods coexist in LiMnPO4·Li3V2(PO4)3/C composite which facilitate the electrolyte penetration. The LiMnPO4·Li3V2(PO4)3/C material exhibits high specific capacity, excellent cycling stability and nice rate capability.