As a new green solvent, deep eutectic solvents (DESs) have been widely studied in the fuel desulfurization industry. This study introduces for the first time a novel three-body DES synthesized from nitromethylpyrrolidone (NMP) as a hydrogen bond acceptor (HBA) and benzoic acid (BEN) and water (H 2 O) as hydrogen bond donors (HBDs). It is also used for extractive desulfurization (EDS) of model oil and analogue FCC gasoline. A Fourier transform infrared ( FT-IR) spectrometer was used to detect the hydrogen bond relationships among NMP, BEN, and H 2 O. The changes in viscosity and density of the three-body DESs also indicated the formation of intermolecular hydrogen bonds among the components and indicated the possible binding forms between the three components of DES. Three-body DESs (NMP/BEN/H 2 O) have higher activity, lower viscosity, and lower volatility than water-deficient two-body DESs (NMP/BEN). By adjusting the mass ratio between the three components and comparing the experimental results of desulfurization, it is shown that the three-body DES (8NMP/2BEN/0.06H 2 O) containing 6 wt % water has the best desulfurization performance, and its four-stage extractive desulfurization rate for the dibenzothiophene model oil (MO-3) can reach 99.8%. The results of this study may expand the application scope of H 2 O and provide a new type of DES for extractive desulfurization of fuel oil and other fields.