Reusable face masks are an important alternative for minimizing costs of disposable and surgical face masks during pandemics. Often complementary to washing, a prolonged lifetime of face masks relies on the incorporation of self-cleaning materials. The development of self-cleaning face mask materials requires the presence of a durable catalyst to deactivate contaminants and microbes after long-term use without reducing filtration efficiency. Herein, we generate self-cleaning fibers by functionalizing silicone-based (polydimethylsiloxane, PDMS) fibrous membranes with a photocatalyst. Coaxial electrospinning is performed to fabricate fibers with a non-crosslinked silicone core within a supporting shell scaffold, followed by thermal crosslinking and removal of the water-soluble shell. Photocatalytic zinc oxide nanoparticles (ZnO NPs) are immobilized on the PDMS fibers by colloid-electrospinning or post-functionalization procedures. The fibers functionalized with ZnO NPs can degrade a photo-sensitive dye and display antibacterial properties against Gram-positive and Gram-negative bacteria (Escherichia coliandStaphylococcus aureus) due to the generation of reactive oxygen species upon irradiation with UV light. Furthermore, a single layer of functionalized fibrous membrane shows an air permeability in the range of 80–180 L/m2s and 65% filtration efficiency against fine particulate matter with a diameter less than 1.0 µm (PM1.0).Graphical abstractSupplementary InformationThe online version contains supplementary material available at 10.1007/s42765-023-00291-7.