The outbreak of Coronavirus Disease 2019 (COVID-19), which is caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), has triggered great global public health concern. Face masks are essential tools to reduce the spread of SARS-CoV-2 from human to human. However, there are still challenges to prolong the serving life and maintain the filtering performance of the current commercial mask. Filters composed of ultrafine fibers with diameter down to tens of nanometers have the potential to physically block viruses. With adjustable composition and nanostructures, the electrospun ultrafine fiber filter is possible to achieve other necessary functions beyond virus blocking, such as antiviral, transparent, and degradable, making it an important part of fighting the epidemic. In this review, beginning with the basic information of the viruses, we summarize the knowledge of masks and respirators, including the filtering mechanism, structure, classification, and standards. We further present the fabrication method, filtering performance, and reusable potential of electrospun ultrafine fiber-based masks. In the end, we discuss the development directions of ultrafine fibers in protective devices, especially their new functional applications and possible contributions in the prevention and control of the epidemic.