Herein, a unique hierarchically structured composite nanofiber membrane, consisting of a zeolitic imidazolate framework-8-embedded polyethersulfone (PES@ZIF8) fiber layer and a polysulfonamide/polyethersulfone (PSA/PES) fiber layer, was successfully developed to cope with the complex environments during the actual filtration/separation process and overcome the conflict between high filtration efficiency and low air pressure resistance. Due to the advantages of the synergistic effect of multicomponents and the bi-layer hierarchical structure, the integrated PES@ZIF8-PSA/PES filter possesses an extremely high air filtration efficiency (up to 99.986%) under a very low pressure drop (only 15 Pa), superior PM0.3 purification capacity (close to 99.95%), long-term recycling ability for purifying real smoke PM2.5 from >800 to <10 μg/m3, extremely high temperature resistance (exceed 200 °C), flame retardancy, good chemical stability, satisfactory transmittance, and robust self-cleaning ability. Apart from these, it achieves effective separation of oil-water mixtures and oil-water emulsions as a result of selective wettability including hydrophobicity and superoleophilicity. In particular, the PES@ZIF8-PSA/PES nanofiber membranes maintain outstanding air filtration and oil/water separation properties under the high temperature or strong acid/alkali conditions. This special comprehensive performance gives the PES@ZIF8-PSA/PES-based filtration/separation membranes a wider application prospect ranging from environmental governance to individual protection and industrial security.