Bacterial infection caused by pathogenic bacteria can occur in the human respiratory tract, skin, blood, and other parts, seriously threatening human life and health. There is an urgent need to develop a durable, internal, fast, and effective sterilization protective mask to limit the proliferation and rapid spread of microorganisms, thereby ensuring human health issues. Therefore, we have ingeniously designed a spherical hollow silver− palladium nanoalloy-based polyacrylonitrile nanofiber film (AgPd-PAN nanofiber film) by the displacement reaction and electrospinning technology, which exhibited an outstanding quad-mode synergistic antibacterial effect. Pd-modified Ag nanospheres, especially AgPd 0.4 , possessed a strong inherent ability to generate reactive oxygen species (ROS). Surprisingly, the synthesized AgPd 0.4 hollow nanospheres showed excellent photothermal conversion performance (28.16%), and the oxidase-like performance of AgPd 0.4 was significantly enhanced under visible light irradiation, resulting in a 20% increase in the production of 1 O 2. The prepared AgPd-PAN nanofiber film also exhibited outstanding photothermal performance, instantly rising to 58.5 °C in 1 min. Meanwhile, the AgPd-PAN nanofiber film had a prominent self-disinfection ability and could completely kill bacteria within 3 h. Notably, once exposed to sunlight, the sterilization time was drastically shortened to 4 min. The rapid production of ROS, the sharp rise of solar irradiation temperature, and the effective release of Ag + contributed to the rapid sterilization of AgPd-PAN nanofiber film. In addition, AgPd 0.4 hollow nanospheres had almost negligible biological toxicity and were suitable for further application in protective equipment. The rapid self-disinfection strategy we designed had great application prospects in the timely sterilization of mask.