This report describes the systematic evaluation of a series of parameters leading to the development of a test procedure for 36 volatile priority pollutants in wastewaters. A study of the effect of pH, temperature, and residual chlorine on the aqueous stability of the compounds leads to recommended preservation techniques. Solvent extraction and purge and trap techniques are examined, with special emphasis on trap material, GC packings and detectors. The resulting test procedures were applied to selected wastewaters to develop accuracy and precision data. The study included the following compounds: benzene, chlorobenzene, toluene, ethylbenzene, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, chloroethane, chloroform, 1,1-dichloroethane, 1,2-trans-dichloroethane, 1,2-dichloropropane, 1,3-cis-dichloropropene, 1,3-trans-dichloropropene, methylene chloride, methyl chloride, methyl bromide, bromoform, dichlorobromomethane, trichlorofluoromethane, chlorodibromomethane, tetrachloroethene, trichloroethene, vinyl chloride, 2-chloroethyvinyl ether, 2,3-dichloropropene, dibromomethane, 1,2-dibromoethane, 1-chlorocyclohexene, p-dichlorobenzene, acrolein, acrylonitrile, dichlorodifluoromethane.