Na and Ti co-doping Li1−x Na x Fe1−x Ti x PO4/C (x =0.00, 0.01, 0.03 and 0.05) composites were synthesized by a simple high-temperature solid-state method. The structure, morphology and electrochemical performance of the samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), charge/discharge tests, electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT). The results showed that the Na and Ti co-doped samples kept the olivine structure of LiFePO4, but Na and Ti co-doping can optimize the crystal microstructure, modify the particle morphology, decrease charge transfer resistance, enhance exchange current density, electrical conductivity and Li ion diffusion velocity, and thus improve the electrochemical performance of the LiFePO4/C. Among all the doped samples, Li0.97Na0.03Fe0.97Ti0.03PO4/C showed the best rate capability and cycling stability. The initial discharge capacity of Li0.97Na0.03Fe0.97Ti0.03PO4/C was 151.0mAhg−1 with the capacity retention ratio of 99.3% after 100 cycles at 1C. Especially, it still showed a high discharge capacity of over 97.3mAhg−1 even at a high rate of 20C.