In recent years, studies of heavy metal air pollution have increasingly gone beyond determining total concentrations of individual toxic metals. Chemical fractionation of potentially toxic elements in airborne particles is becoming an important part of these studies. This review covers the articles that have been published over the last three decades. Attention was paid to the issue of atmospheric aerosol sampling, sample pretreatment, sequential extraction schemes and conditions of individual extractions. Geochemical forms of metals occurring in the air in urban areas were considered in detail. Based on the data sets from chemical fractionation of particulate matter samples by three sequential extraction procedures (SEPs)—Fernández Espinosa, BCR and Chester’s—the compilation of the chemical distribution patterns of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was prepared. The human health risk posed by these toxic and/or carcinogenic elements via inhalation of atmospheric particles was estimated for two categories of polluted urban areas: the commonly encountered pollution level and the high pollution level.