Atmospheric particulate matter (PMs) pollution has raised increasing public concerns, especially with the outbreak of COVID-19. The preparation of high-performance membranes for air filtration is of great significance. Herein, the biosynthetic polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was adopted to create a hierarchical structure and biodegradable nonwoven membrane for PMs filtration through a facile directly electrospinning method. The as-prepared membranes with hierarchical structure contain abundant nanowires (5-100 nm) and microfibers (2-5 μm) with different diameter (1000-5000 nm). We have achieved realization of formation mechanisms of such bimodal micro- and nanofibers, which stem from the branching of microfiber at early stage of electrospinning. The PHBV membranes exhibit a very high PM0.3 removal efficiency of 99.999% and PM2.5 removal efficiency of 100% with 0.077% standard atmospheric pressure in the air flow speed of 5.3 cm/s. More importantly, the PHBV membranes can be completely disintegrated within 1 week under composted conditions, indicating the great biodegradability of PHBV membranes. Our work provides insights for the development of biodegradable, high performance air filters for pollutants, molds, bacteria, and viruses.