The Ni-doped CoFe2O4 graphene composites (Ni-CFO/RGO) have been successfully prepared using the microwave-assisted method. The substance is a novel nanocomposite structure in which CoFe2O4 nanoparticles are tightly and uniformly attached to graphene hybrid nanosheets. The synergistic effect of Ni doping and CoFe2O4 can reduce the volume expansion of CoFe2O4 in the reaction process and inhibit the stacking of graphene. Because the Ni-CFO/RGO composite is structurally stable during the electrochemical reaction, it has a good theoretical capacity. Excellent carbon composite can further enhance the electron transport performance and structural stability of the material, thereby improving the electrochemical performance and cycle life of the material. Doping Ni2+ into metal oxides can not only form oxygen vacancies, and improve the transport capacity of sodium ions, but also broaden the electron transport channel. In addition, the catalyst can form a composite structure with metal oxide, which can effectively inhibit its volume expansion. At the same time, reacting with carbon materials, can also effectively reduce the accumulation of carbon, thereby reducing its resistance. After 200 cycles at a current density of 0.05 A g−1, it can provide a high sodium storage capacity of 380.6 mAh g−1, which still keeps 203.4 mAh g−1 at 1.5 A g−1.