Dispersive liquid-liquid microextraction has garnered increasing attention in sample preparation due to its rapid and efficient extraction process. In this study, a new terpineol-based hydrophobic deep eutectic solvent was firstly synthesized by mixing α-terpineol with 1-octanoic acid, and then applied to analysis of phenols from water samples by dispersive liquid-liquid microextraction combined with high-performance liquid chromatography and diode array detection. Infrared spectroscopy indicated that hydrogen bonding was responsible for the formation of deep eutectic solvent between α-terpineol and 1-octanoic acid. After optimization of several parameters, such as the type and volume of deep eutectic solvent and the disperser, pH and ionic strength of sample solution, the developed method exhibited excellent extraction performance to the phenols with the enrichment factors from 27 to 32. Good linearity was acquired ranging from 5 to 5000 μg/L, and detection of limits of the proposed method for the phenols ranged from 0.15 to 0.38 μg/L. The recoveries measured by spiked samples at three concentration levels ranged from 81.6 to 99.3%, and precision was found with intra- and inter-day relative standard deviations less than 8.7 and 9.2%, respectively. Finally, the proposed method was successfully applied to the determination of the phenols in environmental water samples.