Though Zn-air batteries (ZABs) are one of the most promising system for energy storage and conversion, challenge still persists in its commercial application due to the sluggish kinetics of oxygen reduction/evolution reaction (ORR/OER). Hereby, a polyvinylidene fluoride (PVDF)-assisted pyrolysis strategy is proposed to develop a novel corrugated plate-like bifunctional electrocatalyst using two-dimensional zeolitic imidazolate frameworks (2D ZIF-67) as the precursor. The employed PVDF plays an important role in inheriting the original 2D structure of ZIF-67 and modulating the composition of the final products. As a result, a corrugated plate-like electrocatalyst, high-density Co nanoparticles decorated 2D Co, N, and F tri-doped carbon nanosheets, can be obtained. The acquired electrocatalyst enables efficient active sites and rapid mass transfer simultaneously, thus showing appreciable electrocatalytic performance for rechargeable Zn-air batteries. Undoubtedly, our proposed strategy offers a new perspective to the design of advanced oxygen electrocatalysts.