Herein, Fe-doped Co3O4 (Fe-Co3O4) was prepared to solve the issues of poor electrical conductivity and the lack of active sites in Co3O4 materials. Due to having similar radius and physical/chemical properties to Co, Fe is an ideal choice for doping Co3O4, as it can improve intrinsic conductivity without causing severe lattice distortion. Oxygen vacancies are gradually formed as doping reactions occur to maintain electric neutrality. Owing to the merits of oxygen vacancies in Co3O4, the distribution of the electrons is changed, thus optimizing the material's intrinsic charge/ion states and modifying the band gap by introducing impurity levels. Moreover, the surface area of Fe-Co3O4 is 1.5 times larger than that of the original material. The synergistic effect promotes the electrochemical oxidation reduction reaction and improves the capacitance and cycling stability. Finally, such an advanced Zn//Fe-Co3O4 battery exhibits a discharge-specific capacity of 171.97 mA h g-1, nearly eight times higher than that of the previous Zn//Co3O4 battery (22.38 mA h g-1). In addition, the attenuation of the capacity was almost negligible after 9000 cycles.