The range of application of static headspace‐gas chromatography to the EPA priority pollutants is examined by calculating theoretical distribution coefficients from vapor pressure and aqueous solubility data reported in the literature. The estimated headspace gas concentrations are then compared to instrument detection limits for flame ionization, Hall electrolytic conductivity, and electron capture detectors to provide a guide to the chromatographer who desires to determine several priority pollutants at 5 μg/l or higher concentrations with the headspace technique.