To minimize the growing concerns of adverse air pollution, many efforts have been devoted to develop filters to filtrate airborne particles. However, the development of a filter with high filtration efficiency and low air resistance is challenging. In this study, we have successfully developed polyvinylidene fluoride (PVDF) hollow fibers with an ultra-high gas permeance for air filtration applications. By using dilute PVDF dopes with SiO2 additives and applying KOH etching processes, the N-2 permeance of resultant hollow fibers increases significantly. The optimized PVDF6.5/SiO2-0.25 hollow fiber, made from 6.5% PVDF dopes containing 25 wt% of SiO2 to PVDF, displays a N-2 permeance of 8.1 x 10(5) GPU after the KOH treatment. Moreover, the KOH treated PVDF6.5/SiO2-0.25 hollow fiber shows filtration efficiency of 99.9999% against both sodium chloride (NaCl) particles and bis(2-ethylhexyl) sebacate (DEHS) particles. Importantly, the filtration efficiency remains at 99.9999% over continuous 36-h filtration experiments under a highly polluted situation with a very small increment in a pressure drop of 100 Pa. Therefore, the proposed methods allow us to fabricate hollow fibers with an ultra-high gas permeance and excellent air filtration performance. The newly designed PVDF hollow fiber may have great potential to be a filter media for air filtration applications.