Herein, a novel technology named coaxial electro‐spraying/electrospinning was successfully introduced, which can simultaneously prepare nanofibers and nanoparticles. First, the device contains an outer nozzle and an inner nozzle, which combine electrospinning with electro‐spraying technology. Then, the polyamide 6 (PA6) was spun to prepare the nanofibers from the inner nozzle, and the silver nanoparticles (Ag NPs) into the PA6 solution were sprayed to prepare the nanoparticles from the outer nozzle. PA6 nanofibers (NFs)/Ag nanoparticles (NPs) antibacterial composite membranes for the filtration of fine particulate pollutants were successfully prepared using coaxial electro‐spraying/electrospinning. The microstructure, physical properties, and antibacterial properties of the composite membrane were investigated. The results show that Ag NPs are successfully loaded in situ onto PA6 NFs of approximately 100 nm to form a three‐dimensional (3D) structure. The filtration efficiency of the 3D structured filtration membrane reaches 90.98%, compared to only 12.78% for the melt‐blown cloth mask filter material when tested with polystyrene microspheres (PS) of 200 nm. The contact angle of the composite membrane decreased from 145.47° to 44.11°, indicating a significant improvement in the hydrophilicity of the membrane. Furthermore, depositing Ag on the surface fibers resulted in an impressive antibacterial rate of 99.75% against Penicillium.