The study on elemental speciation in atmospheric particulate matter (PM) is important for understanding the formation and origin of pollution and evaluating their toxicity. In this paper, the speciation of iron in atmospheric PM was investigated with extended X-ray absorption fine structure (EXAFS) spectra based on synchrotron radiation. The chemical components of PM can be calculated by regression analysis of EXAFS spectra. This is a non-destructive method. In order to have knowledge of the influence of chemical components on EXAFS spectra, we prepared a series of mixed reference samples, and proved the precision of method is good. The PM samples with different particle sizes and from different sampling sites were collected in Shanghai, China. The chemical components of the samples were calculated by regression analysis of EXAFS spectra. The results show that the iron in all PM samples mainly consist of Fe2O3, Fe3O4 and Fe2(SO4)3, but their proportions are different in different samples. The changes of components among PM samples were observed preliminarily. The concentrations of iron in the samples were determined by proton-induced X-ray emission (PIXE) technique. It is observed that the concentrations of iron in the samples of iron and steel industrial district were much higher than those of other districts, and chemical components were also different from those of others.