The broad application of plastic products has resulted in a considerable release of microplastics (MPs) into the ecosystem. While MPs in other environmental matrices (e.g., soil and water) have been studied for a long time, the atmospheric fine particulate matter (PM 2.5 )bound MPs are rarely investigated due to the lack of an appropriate analytical approach. The prevalently used visual and spectroscopic means (e.g., optical microscopy, Fourier-transform infrared spectroscopy, and Raman spectroscopy) suffer from obvious drawbacks that cannot precisely detect MPs of tiny sizes and provide quantitative information. In the present study, a novel strategy that does not require sample pretreatment was developed to first effectuate accurate quantification of polyethylene MP (PE-MP) in PM 2.5 based on pyrolysis-gas chromatography−tandem mass spectrometry (Pyr-GC-MS/MS). It featured acceptable recoveries (97%−110%), high sensitivity (LOD = 1 pg), and qualified precisions (RSD of 3%−13%). Employing this approach, for the first time, exact atmospheric concentrations of PE-MPs in PM 2.5 from megacities in North (Zhengzhou and Taiyuan) and South (Guangzhou) China were obtained, and relatively serious pollution was found in Taiyuan. The 100% sample detection rates also suggested the widespread occurrence and possible human exposure risks of PM 2.5 -bound PE-MPs. In brief, the new strategy could conduct direct, sensitive, and accurate quantification of PE-MP in PM 2.5 , favoring further studies of environmental fates, distributions, and toxicities of atmospheric MPs.