A high proportion of the total microplastic (MP) load in the marine environment has been identified as microfibers (MFs), with polyester (PET) and polyamide (PA) typically found in the highest abundance. The potential for negative environmental impacts from MPs may be dependent on their degree of degradation in the environment, which is influenced by both intrinsic properties (polymer type, density, size, additive chemicals) and extrinsic environmental parameters. Most polymer products break down slowly through a combination of environmental processes, but UV degradation can be a significant source of degradation. The current study aimed to investigate the effect of UV irradiance on the degradation of natural (wool) and synthetic (PET and PA) MFs. Degradation of MFs was conducted in seawater under environmentally relevant accelerated exposure conditions using simulated sunlight. After 56 days of UV exposure, PA primarily exhibited changes in surface morphology with no significant fragmentation observed. PET and wool fibers exhibited both changes in surface morphology and fragmentation into smaller particles. A range of molecular degradation products were identified in seawater leachates after UV exposure, with increasing abundance over the duration of the experiment. Furthermore, a variety of additive chemicals were shown to leach from the MFs into seawater. While some of these chemicals were also susceptible to UV degradation and some are expected to biodegrade rapidly, others may be persistent and contribute to the overall load of chemical pollution in the marine environment.