Vortex-assisted dispersive liquid-liquid microextraction based on the solidification of sedimentary deep eutectic solvents was developed and applied to the extraction of triazine and phenylurea herbicides in milk samples. In this study, a series of novel hydrophobic deep eutectic solvents were prepared using tetrabutylammonium chloride as the hydrogen bond acceptor and perfluorooctanol as the hydrogen bond donor, and their structures, viscosities, densities and melting points were determined. The deep eutectic solvent was used as the extraction solvent and dispersed in the sample solution with the assistance of vortex. After extraction, through centrifugation and subsequent cooling in an ice bath, the deep eutectic solvent was solidified and deposited on the bottom of the centrifuge tube. Subsequently, the deep eutectic solvent combined with the target analytes was diluted and used for chromatographic analysis. Some parameters, including the extraction temperature, type and volume of the deep eutectic solvent, amount of NaCl, vortex time and pH of the sample solution, were optimized by the single-factor experiment, Plackett-Burman design and Box-Behnken design. The limits of detection and quantification were in the range of 0.41-0.59 μg L-1 and 1.37-1.95 μg L-1, respectively. The intra-day precision and inter-day precision were in the range of 0.28-2.14% and 2.02-7.99%, respectively. The present method was successfully applied to the determination of triazine and phenylurea herbicides in milk samples.