The pristine LiFePO4/C and Ni and Mn co-doping LiFe1−x−y Ni x Mn y PO4/C (x = 0.01–0.04; y = 0.04–0.01) composites are synthesized for the first time by a simple high-temperature solid-state route. The structure, morphology and electrochemical performance of the samples are characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, scanning electron microscope (SEM), charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results indicate that the Ni and Mn co-doping does not destroy the olivine structure of LiFePO4, but it can stabilize the crystal structure, lengthen the Li–O bond, decrease charge transfer resistance, enhance Li ion diffusion velocity, and thus improve its cycling and high-rate capability of the LiFePO4/C. Especially, the LiFe0.95Ni0.02Mn0.03PO4/C shows the best cycling stability and rate capability among all the doped samples. The first discharge capacity of LiFe0.95Ni0.02Mn0.03PO4/C is 145.4 mAh g−1 with the capacity retention ratio of 98.6% till 100 cycles at 1C. Even at a high rate of 10C, it still reveals a high discharge capacity of 115.2 mAh g−1.