More than 90% of the 75,000 chemicals listed in EPA's Toxic Substances Control Act Chemical Substance Inventory and 88% of the 189 Hazardous Air Pollutants (HAPs) named in the Clean Air Act Amendments of 1990 are organic. Methods for collecting organic chemicals from the air for analysis are often complicated and depend on the volatility of the compounds, as well as other chemical and physical properties. The various methods of sampling airborne organics are reviewed and discussed here and 275 literature citations are given. Special sampling difficulties associated with chemical behavior in the atmosphere, such as reactivity and phase distribution, are discussed. The pros and cons of sampling devices, sorbents, and other sampling parameters are presented in the context of chemical type, with special application to the Clean Air Act HAPs. The elements of good quality assurance practice in organic chemical air sampling are also discussed.