Volatile halogenated organic chemicals are found in indoor and outdoor air, often at concentrations substantially above those in remote, unpopulated areas. The outdoor ambient concentrations vary considerably among sampling stations throughout the United States, as well as diurnally and daily. The vapor pressures and air-water equilibrium (Henry's Law) constants of these chemicals influence considerably the likely relative human exposures for the air and water routes. Volatilization of chemicals from indoor uses of water can be a substantial source of exposure, as shown for radon-222. Measurements of air concentrations of trichlorethylene (TCE) in showers using TCE contaminated groundwater show increases with time to as high as one-third of occupational threshold limit values. Using a scaled down experimental shower, such volatilization and subsequent decay in air was also demonstrated. Using a simplified indoor air model and assuming complete volatilization from a full range of typical water uses within the home, calculations indicate that the expected air inhalation exposures can be substantially higher than those from ingestion of these chemicals in drinking water. Although the regulation of toxic chemicals in potable water supplies has focused traditionally on direct ingestion, the volatilization and inhalation from other much greater volume indoor uses of water should be considered as well.