The rational design of multiphasic interfaces is an efficient way to fabricate favorable catalysts for bifunctional oxygen reduction and oxygen evolution reactions (ORR/OER). Herein, the hybrid metallic nanoparticles composed of Co, CoO, and Cedoped WO 3 are anchored on the external surface of the preprepared catalysts (PZF-2-700) by pyrolyzing a unique polyoxometalate (POM)-containing metal−organic framework (MOF) precursor. The multiple heterointerfaces in the PZF-2-700 material surface provide defects as the catalytic active sites for the OER. Besides, the Co and CoO with Co−N−C, N−C, and Co−O in PZF-2-700 afford efficient catalytic performance for the ORR. Furthermore, the strong built-in field of PZF-2-700 enables the heterointerfaces with opposite charges and facilitates the electron transfer capacity throughout the structure. Based on this, the produced PZF-2-700 exhibits a small potential gap of 679 mV between the ORR and the OER. The homemade zinc−air battery (ZAB) with PZF-2-700 as the cathode catalyst displays a power density of 146.9 mW cm −2 and a charge/discharge cycling stability for 311 h with a charge−discharge period of 10 min, which offers a promising cathode catalyst for environment-friendly ZABs.