As a first attempt, cloud point extraction (CPE) was developed to preconcentrate bisphenol A (BPA), α-naphthol and β-naphthol prior to performing capillary zone electrophoresis (CZE) analysis. The parameters influencing the CPE efficiency, such as Triton X-114 concentrations, pH value, extraction time and temperature were systematically evaluated. After diluting with acetonitrile, the surfactant-rich phase of CPE can be injected directly into the CE instrument. The CZE baseline separation was achieved with running buffer (pH 9.5) composed of 50mM sodium tetraborate in 30% (v/v) methanol, and an applied voltage of 25 kV. Under the optimized CPE and CZE conditions, an preconcentration factor of 50 times could be obtained and the limit of quantification for the three analytes were found to be 1.67 μg L(-1), 0.80 μg L(-1) and 0.67 μg L(-1) for BPA, α-naphthol and β-naphthol, respectively. The proposed methods have shown to be a green, rapid and effective approach for determination of three analytes present in river water samples.