Global environmental problems are facing serious challenges, especially the harm of air pollution to human health. It is meaningful to capture harmful particulate matter (PM) in the air. In this work, we report for the first time the facile synthesis of porous organic polymers (POPs) with macroporous structure, which were synthesized using 1,4-benzenedithiol, 1,4-diethynylbenzene and 1,3-benzenedithiol via click chemistry, for efficient PM capture. PM filtration measurement was simulated by the release of particulate pollutants from cigarette smoke. The test results of porous composite membranes (PCMs) show a high PM removal efficiency for PM2.5 (≥99.80 ± 1.58%) and PM10 (≥99.89 ± 0.89%) in 30 h. The PCMs based on kapok fiber not only has good mechanical properties, but also can be made into membranes of different sizes depending on the size of the substrate. Taking advantage of their simple one-step synthesis via click chemistry with great potentials for scale-up under mild conditions, such PCMs may find useful applications in PM capture. © 2020