<p>Hydrophobic deep eutectic solvent (HDES) synthesized from trioctylmethyl ammonium chloride (N263) and ethyl p-hydrobenzoate (EP) was used to separate and enrich valuable metals from cyanide gold extraction wastewater. The effects of the molar ratios between N263 and EP, the oscillation time, the initial pH of the aqueous phase, the phase ratio (O/A), and the temperature on the total cyanide removal percentage and metal extraction percentage were mainly investigated. It was shown that under the conditions of N263/EP molar ratio of 2:1, oscillation time of 3&#xa0;min, pH of 9, O/A of 1:10, and temperature of 25&#xa0;°C, the removal percentage of CN_T in wastewater reached 98.57%, and the single-stage extraction percentage of Zn and Cu could reach 99.62% and 99.96%, and the saturated extraction capacities were 73,317.5&#xa0;mg/L and 33,671.1&#xa0;mg/L, respectively. The loaded organic phase was successively stripping using NH₄OH solution and KSCN solution under the condition of O/A of 3, and the stripping percentage of Zn and Cu were 98% and 99.89%, respectively, which realized the effective enrichment and separation of the metal cyanide complex ions. During the synthesis process of HDES, the intermolecular hydrogen bonding was formed between the Cl⁻ in the N263 and the H in the -OH group in the EP. During the extraction process, Cu(CN)₃²⁻ and Zn(CN)₄²⁻ with lower charge density undergo an ion exchange reaction with Cl⁻ in HDES. They combine with N⁺ in HDES through electrostatic interaction and are encapsulated in the organic phase in the form of two ligands.</p> Graphical Abstract <p></p>