A novel approach was developed for the determination of ultratrace amounts of copper in water samples by using electrothermal atomic absorption spectrometry(ETAAS) after cloud point extraction(CPE). 1-(2-Pyridylazo)-2-naphthol was used as the chelating reagent and Triton X-114 as the micellar-forming surfactant. CPE was conducted in a pH 8.0 medium at 40 ℃ for 10 min. After the separation of the phases by centrifugation, the surfactant-rich phase was diluted with 1 mL of a methanol solution of 0.1 mol/L HNO3. Then 20 μL of the diluted surfactant-rich phase was injected into the graphite furnace for atomization in the absence of any matrix modifier. Various experimental conditions that affect the extraction and atomization processes were optimized. A detection limit of 5 ng/L was obtained after preconcentration. The linear dynamic range of the copper mass concentration was found to be 0_2.0 ng/mL, and the relative standard deviation was found to be less than 3.1% for a sample containing 1.0 ng/mL Cu(Ⅱ). This developed method was successfully applied to the determination of ultratrace amounts of Cu in drinking water, tap water, and seawater samples. A novel approach was developed for the determination of ultratrace amounts of copper in water samples by using electrothermal atomic absorption spectrometry (ETAAS) after cloud point extraction (CPE). 1- (2-Pyridylazo) -2-naphthol was used as the chelating reagent and Triton X-114 as the micellar-forming surfactant. CPE was conducted in a pH 8.0 medium at 40 ° C for 10 min. After the separation of the phases by centrifugation, the surfactant-rich phase was diluted with 1 mL of a methanol solution of 0.1 mol / L HNO3. Then 20 μL of the spent surfactant-rich phase was injected into the graphite furnace for atomization in the absence of any matrix modifier. Various experimental conditions that affect the extraction and atomization processes were optimized. A detection limit of 5 ng / L was obtained after preconcentration. The linear dynamic range of the copper mass concentration was found to be 0_2.0 ng / mL, and the relative standard deviation was found to be less than 3.1% for a sample contain ing 1.0 ng / mL Cu (II). This developed method was successfully applied to the determination of ultratrace amounts of Cu in drinking water, tap water, and seawater samples.