Cation doped LiFePO₄/graphene composites with dopant Ti, Zr, or Nb were prepared by solid-state reaction. The as prepared composites were characterized by X-ray diffraction and scanning electron microscopy. Their electrochemical properties were investigated by cycling charge and discharge measurements at various C-rate, cyclic voltammetry, and electrochemical impedance spectroscopy. The experimental results reveal the combined effects brought by cation doping and graphene addition on LiFePO₄.