A pyrolyzed carbon and reduced graphene oxide co-doped LiMn0.9Fe0.1PO4 (LMFP/C/rGO) is synthesized by a novel and facile amine-assisted coating strategy. The well designed co-doped LiMn0.9Fe0.1PO4 nanoplate (LMFP/C/rGO, 150 nm in length and 20 nm in thickness) is proved to be olivine phase with good crystallinity which is further compared with the sole pyrolyzed carbon coated LiMn0.9Fe0.1PO4 (LMFP/C) from structural and electrochemical points of views. The LMFP/C/rGO exhibits superior electrochemical performances with the specific capacity of 158.0 mAh g−1 at 0.1C and 124.6 mAh g−1 at 20C, which is, to the best of our knowledge, the highest rate capability. Moreover, after 140 cycles at 0.2C rate, around 95% of the initial capacity is still retained. Further analyses disclosed the outstanding electrochemical performances can be ascribed to the collaboration of the uniformly coated pyrolyzed carbon and closely connected rGO with an extraordinary electronic conductivity. Our research shows this effective synthesis strategy is imperative for the improvement of Li-ion battery performance and can be widely used for advanced energy storage.