Recycling of valuable metals from spent catalysts in a green way is gaining extensive interest for economic and environment reasons. In this study, we developed novel hydrophobic deep eutectic solvents to extract Mo from spent catalysts. The hydrophobic DESs have been designed and synthesized by mixing one molar of the quaternary ammonium salt and two molars of various saturated fatty acids with different carbon chain lengths. The extraction ability and extraction mechanism of these DESs were studied, some factors influencing the extraction efficiency, including the structure of hydrogen bond acceptors and hydrogen bond donors, initial aqueous pH, reaction time and temperature, phase ratios were investigated. It is found that the synthesized hydrophobic DESs exhibit excellent extraction performance toward Mo, where the Mo distribution ratio is more than 2200 in the presence of other metals, corresponding to an extraction efficiency of 99% at optimal reaction conditions. This work reveals a distinct class of materials, guiding an effective and green way for spent catalyst treatment.Implications: Novel hydrophobic deep eutectic solvents have been developed to extract Mo from spent catalysts, the synthesized hydrophobic DESs possess several advantages, such as green, low price, low toxicity, and biodegradability. It exhibits excellent extraction performance under an optimized extraction condition. This work reveals a distinct class of materials, guiding a promising way for green and economical utilization of spent catalysts.