Airborne radioactive iodine is a key concern for the transport and dispersion of radioactive contamination and radiation exposure evaluation during nuclear accidents and nuclear emergency preparedness. Information about long-lived 129I in aerosols is vital for the reconstruction of the level and distribution of short-lived and highly radiotoxic 131I, as well as for understanding the atmospheric cycling of iodine. However, aerosol 129I concentration is difficult to measure due to its low concentration in remote areas, away from nuclear pollution sources. In this study, a novel method for the determination of 129I in aerosols collected on a glass fiber filter was developed using high-temperature pyrolysis and AgI-AgCl coprecipitation for separation coupled with highly sensitive accelerator mass spectrometry (AMS) measurements. It is worth noting that even though the pyrolysis behaviors of various iodine species were investigated and found to be different, all of the iodine can be quantitatively recovered. Iodate was released from the aerosols through its decomposition to iodine at temperatures over 500 °C. The chemical yield of iodine during pyrolysis was 81.5 ± 5.8%. The detection limit for 129I in the aerosol samples was 1.3 × 104 atoms per m3, at least reducing the required aerosol sample size by a factor of three, in contrast to the method using alkaline-ashing separation coupled to solvent extraction. For aerosol samples collected in Asia with129I/127I ratios of (0.1-10) × 10−9, a volume of 1000 m3 air is sufficient for the determination of129I. The developed method was used to analyse aerosol samples collected in Xi'an, an inland Chinese city. It is observed that 129I concentrations ranged within (0.38-5.19) × 105 atoms per m3, with129I/127I ratios of (21.7-252) × 10−10, which are comparable to those collected in Japan before the Fukushima nuclear accident and Spain, while much lower than those observed in Northern Europe.