MnFe2O4/reduced graphene oxide nanocomposite (MnFe2O4/rGO) has been synthesized via a green reduction-coprecipitation method for the first time, which involved in situ reduction of GO in presence of Fe2+ and the ensuing coprecipitation of Fe3+ and Mn2+ onto the surface of rGO. The resultant MnFe2O4/rGO was then employed as the precursor to fabricate LiMn1/3Fe2/3PO4/reduced graphene oxide/carbon composite (LiMn1/3Fe2/3PO4/rGO/C) cathode material for Li-ion batteries. The composite consists of homogeneous Mn-Fe distributed LiMn1/3Fe2/3PO4 with its primary particles (∼200nm) covered and connected by both pyrolytic carbon and rGO sheets, which could prevent the aggregation of the particles as well as construct an interconnected conductive network for rapid transmission of electrons during charging and discharging process. The fabricated LiMn1/3Fe2/3PO4/rGO/C can deliver a discharge capacity of 94.8mAhg−1 even at the high rate of 20C, and shows a capacity decay rate of only 6.25% after 900 long-term charge-discharge cycles. Moreover, the proposed synthesis strategy can also be applied to prepare other graphene-decorated multi-component cathode/anode materials for the Li-ion batteries.