The work aims to prepare a daylight-driven antibacterial nanofiber membrane, in order to develop a low-energy and low-cost food preservation method. The polyvinyl alcohol (PVA) nanofiber membrane was prepared by the combination of electrospinning and photosensitive chemicals. The nanofiber membrane was characterized by scanning electron microscopy, Fourier infrared spectroscopy, thermogravimetric analysis, water contact angle, water resistance test, release of active oxygen and antibacterial experiment. The photosensitive benzophenone tetracarboxylic dianhydride (BTDA) was successfully grafted on the PVA nanofiber membrane and released active oxygen under the driving of daylight, which could effectively kill pathogenic bacteria. In conclusion, the nanofiber membrane can effectively produce active oxygen under the driving of daylight, thereby killing microorganisms. Therefore, it will be newly applied to antibacterial food packaging.