Zinc oxide (ZnO) nanostructures have received widespread attention due to their unique structure and broad application possibilities, but high preparation costs and agglomeration limit their usage. In this article, low-cost and environmentally friendly cellulose and ZnCl2 are used to synthesize ZnO nanoparticles (ZnO NPs). Subsequently, multifunctional ZnO/polyacrylonitrile hybrid nanofiber mats (ZnO/PAN@NFMs) with mechanical stability suitable for large-scale application are prepared via solution blow-spinning. The synthesized ZnO/PAN@NFMs exhibit higher photodegradation of organic dyes than earlier reported semiconductors and good recycling performance with an organic dye degradation above 94%–98% after five cycles, which is ascribed to fixation of the ZnO NPs in the nanofibers. In addition, the inhibition rate for Escherichia coli and Staphylococcus aureus is above 99.9% and the bacteriostatic rate against E. coli remains as high as 99% after 10 cycles. From these properties, the synthesized composite ZnO/PAN@NFMs are promising for wastewater cleaning and antibacterial fabrics.