High-entropy alloy (HEA)-based materials are expected to be promising oxygen electrocatalysts due to their exceptional properties. The electronic structure regulation of HEAs plays a pivotal role in enhancing their elctrocatalytic ability. Herein, PtFeCoNiMn nanoparticles (NPs) with subtle lattice distortions are constructed on metal-organic framework-derived nitrogen-doped carbon by an ultra-rapid Joule heating process. Thanks to the modulated electronic structure and the inherent cocktail effect of HEAs, the as-synthesized PtFeCoNiMn/NC exhibits superior bifunctional electrocatalytic performance with a positive half-wave potential of 0.863 V vs. reversible hydrogen electrode (RHE) for oxygen reduction reaction and a low overpotential of 357 mV at 10 mA·cm^–2 for oxygen evolution reaction. The assembled quasi-solid-state zinc-air battery using PtFeCoNiMn/NC as air electrode shows a high peak power density of 192.16 mW·cm^–2, low charge−discharge voltage gap, and excellent durability over 500 cycles at 5 mA·cm^–2. This work demonstrates an effective route for rational design of bifunctional nanostructured HEA electrocatalysts with favorable electronic structures, and opens up a fascinating directions for energy storage and conversion, and beyond.