A simple, efficient, solvent-free, and commercial readily available approach for determination of 11 chlorobenzenes (CBs) in water samples using the static headspace (HS) sampling and gas chromatography-electron capture detector has been described. The proposed static HS sampling method was initially optimized and the optimum experimental conditions found were 10 mL water sample containing 20% (w/v) sodium chloride placed in a 20 mL vial and stirred at 70°C for 30 min. The linearity of the method ranged from 0.16 to 8.0 μg/L for dichlorobenzene isomers, 0.0176~0.88 μg/L for trichlorobenzene isomers, 0.004~0.2 μg/L for tetrachlorobenzene isomers, and from 0.001 to 0.05 μg/L for pentachlorobenzene and hexachlorobenzene, with correlation coefficients ranging between 0.9992 and 0.9999. The limits of detection were in the low μg/L level, ranging between 0.0002 and 0.04 μg/L. The relative recoveries of spiked CBs with external calibration or standard addition method at different concentration levels in pure, tap, and sea water samples were 83~116%, 89~108%, and 93~112%, respectively, and with relative standard deviations of 1.9~6.3%, 1.6~5.4%, and 2.5~5.7% (n = 5), respectively. It is concluded that this method can be successfully applied for the determination of CBs in pure, tap, and sea water samples.