Single-use face masks can release microfibres upon exposure to environmental conditions. This study investigates the number of microfibres released in the presence and absence of UV irradiation and mechanical friction and the removal of the released microfibres in a simulated conventional wastewater treatment process. UV exposure results in a four-fold increase in the number of microfibres released from new masks and used masks resulting in ~2400 microfibres/mask and ~1100 microfibres/mask, respectively. Application of mechanical friction to the UV-exposed new and used masks further increases the number of released microfibres per mask. In a simulated coagulation/flocculation process, the removals of microfibers originating from new masks and used masks are 79% and 91%, respectively. XPS analysis reveals that the silica content of the used masks is 240% higher than that of new masks, which could explain the higher removal efficiency of microfibers from used masks. FTIR analysis of the masks after UV exposure shows carbonyl indices of 0.73 ± 0.70 and 0.27 ± 0.10 for the microfibres from used and new masks, respectively. Based on available data, we estimate that 4–47 million polypropylene microfibres can be released into natural waters per day after wastewater treatment in an urban environment (for a population of 4300 persons/km²).