A microextraction based on pH‐responsive deep eutectic solvent combined with high‐performance liquid chromatography was developed for the separation, preconcentration, and determination of bisphenol A in water samples. Five deep eutectic solvents were prepared using thymol (hydrogen bond acceptor) and 6‐, 8‐, 9‐, 10‐, and 12‐carbon carboxylic acids (hydrogen bond donor), and were used as extraction solvent. Herein, by alkalinizing the environment, phase transition takes place, and by adding acid, phase separation and extraction of analytes occur simultaneously. Some important parameters on the extraction such as deep eutectic solvent type, molar ratio of deep eutectic solvent components, deep eutectic solvent volume, potassium hydroxide concentration, hydrochloric acid volume, extraction time, and salt addition were optimized. Under the optimum conditions, intra‐ and interday precisions of the method based on seven replicate measurements of 10 μg L–1 of bisphenol A in water samples were 2.2% and 4.3%, respectively. The analytical performance of the method showed linearity over the concentration of 0.05–50 μg L−1 with the detection limit of 0.02 μg L−1. The accuracy of the method was confirmed by spiking different concentrations of bisphenol A in real water samples and obtaining relative recoveries in the range of 92.5%−105.2%.