The invention relates to a multilayer composite nanofiber film and an application thereof. The composite fiber film has high retention efficiency and low resistance, and can be widely applied to the fields of air purification, oil and water separation, desalination of feed liquid, etc. The nanofiber film with a multilayer composite structure is prepared by macromolecular nanofiber of different diameters, the diameters gradually change from 10 nanometer to 10[mu]m, the separating functions change from low efficiency to high efficiency, removal rates for PM2.5 and PM10 dust particles reach 100%, and the removal rate for phage reaches above 99.9%. Water flux in a process of membrane distillation reaches 10-100LMH, and the salt rejection rate reaches above 90%. The nanofiber film can be used for treating oil-containing waste water, and the oil removing efficiency reaches above 90%.
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