A deep eutectic solvent (DES) was prepared using o-cresol and acetic acid as hydrogen bond acceptor and hydrogen bond donor, respectively, and used for the simultaneous extraction of different chlorophenols from water samples. With dispersive liquid–liquid microextraction based on the solidification of DES (DLLME-DES), different key parameters including the type of dispersing solvent, the effect of pH, volume of DES, and dispersing solvent, as well as the volume of the derivatization reagent were investigated to reach the maximum extraction efficiency. The limits of detection and quantification were in the range of 0.015–1.0 µg/L and 0.05–3.0 µg/L, respectively. Chlorophenols recoveries from water samples spiked at different concentration levels were 32–91% (RSD ≤ 5.8%). Satisfactory repeatability values were 1.7–5.8% through analyzing seven replicates of chlorophenols standards at concentration levels of monochlorophenols 200 µg/L, dichlorophenols 100 µg/L, trichlorophenols 4.0 µg/L, tetrachlorophenols, and pentachlorophenols 2.0 µg/L.