1,4-Dioxane is used as a solvent for lacquers, paints, varnish removers, dye baths and printing compositions. And it is also used for detergent preparations, cosmetics, deodorants and fumigants. A method is described for the determination of 1,4-dioxane in water samples by GC/MS. The extraction recoveries were studied for some solvents and solvent volume ratio were investigated using t-butyl methyl ether(MTBE). Optimum condition was obtained by the liquid-liquid extraction using the 10 mL of MTBE for 10mL of water. Method detection limit of 1,4-dioxane in the 20mL of water samples was 0.05 ng/mL. It could be determined in the range of 0.24~240 ng/mL in treated water, and in the range of 0.69~81.9 ng/mL in raw water, respectively. Risk assessments with 1,4-dioxane exposure by drinking water ingestion were carried out. Based on the results of analysis, chronic daily intake of 1,4-dioxane was 2.22×10^(-4) mg/kg/day and excess cancer risk was calculated to be 2.44×10^(-6).