AbstractAir pollution is caused by the perilous accumulation of particulate matter (PM) and harmful gas molecules of different sizes. There is an urgent need to develop highly efficient air filtration systems capable of removing particles with a wide size distribution. However, the efficiency of current air filters is compromised by controlling their hierarchical pore size. Inspired by the graded filtration mechanisms in the human respiratory system, microporous ZIF‐67 is in situ synthesized on a 3D interconnected network of bamboo cellulose fibers (BCFs) to fabricate a multiscale porous filter with a comprehensive pore size distribution. The macropores between the BCFs, mesopores formed by the BCF microfibers, and micropores within the ZIF‐67 synergistically facilitate the removal of particulates of different sizes. The filtration capabilities of PM2.5 and PM0.3 could reach 99.3% and 98.6%, respectively, whereas the adsorption of formaldehyde is 88.7% within 30 min. In addition, the filter exhibits excellent antibacterial properties (99.9%), biodegradability (80.1% degradation after 14 days), thermal stability, and skin‐friendly properties (0 irritation). This study may inspire the research of using natural features of renewable resources to design high‐performance air‐filtration materials for various applications.