Facemasks are indispensable for preventing the spread of COVID-19. However, improper disposal of discarded facemasks has led to their contamination in the marine environment. To understand the environmental risk of this emerging plastic pollution, it’s important to clarify the features that distinguish discarded facemasks from common plastic waste during aging. This study compared the microbial colonization, degradation-related enzymes, and physicochemical properties among surgical masks, polystyrene cups, polycarbonate bottles, and polyethylene terephthalate bottles in their aging processes in natural seawater. Compared to the other plastic wastes, surgical masks were colonized by the most diverse microorganisms, reaching 1521 unique prokaryotic OTUs after 21-day exposure in seawater. Moreover, the activity of eukaryotic enzymes associated with plastic degradation was 80-fold higher than that in seawater, indicating that the colonized eukaryotes would be the major microorganisms degrading the surgical masks. Meanwhile, the nano-sized defects (depth between 8 and 61 nm) would evolve into cracks of bigger sizes and result in the breakage of the microfibers and releasing microplastics into the ocean. Overall, our study demonstrated a distinctive plastisphere occurred in surgical masks from both microbial and physiochemical aspects. This work provides new insights for assessing the potential risk of plastic pollution caused by the COVID-19 pandemic.