Herein, a class of Co₃S₄@Co₃O₄/NSC (N, S-doped carbon) composites with core@shell nanostructures were facilely fabricated through a two-step pyrolysis-oxidation strategy using methyl orange and cobalt chloride as raw materials. By constructing heterointerfaces between different components and controlling the surface oxidation degree, the interfacial and synergistic effects endowed the composited catalysts tailorable and excellent bifunctional electrocatalytic activities on oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A rechargeable Zn-air battery (ZAB) with the optimized catalyst Co₃S₄@Co₃O₄/NSC-260-8 as air cathode has shown excellent performance with a high specific capacity of 885 mAh·g_Zn⁻¹ and energy density of 948 Wh·kg_Zn⁻¹ (at 20 mA·cm⁻²), which is higher than 836 mAh·g_Zn⁻¹ and 929 Wh·kg_Zn⁻¹ of the one employing Pt/C (20%) + RuO₂ as air cathode under the same conditions. The catalyst also showed robust stability and no obvious decrease in the voltage was observed after 200 h charging and discharging cycles. This work presents a feasible concept to design and construct heterostructural and multifunctional composite catalysts with heterointerfaces.