A new type of composite adsorbent, MOF-5/Cu(I), was prepared by MOF-5 doped with different amount of CuCl using a spontaneous monolayer dispersion technique. These new composite adsorbents were characterized by X-ray diffraction, thermogravimetric analysis, electrondispersion X-ray scope, and N-2 adsorption, respectively. The desulfurizaion performance of the prepared adsorbents was evaluated by the selective adsorption of dibenzothiophene from the simulated oils in a fixed-bed breakthrough column at room temperature. From the obtained breakthrough curves, both the breakthrough capacity and the saturation capacity of the adsorbents for sulfur element were determined. The results show that MOF-5/Cu(I) exhibited high desulfurization capacities, which are superior to those reported previously in the literature. In addition, these novel composite adsorbents possessed good durability and affinities for the adsorption of dibenzothiophene in the presence of aromatic components and moisture. The saturated composite adsorbent MOF-5/Cu(I) can be regenerated with nitrogen atmosphere sweeping at 623 K for 4 h. About 97% of the desulfurization capacity was recovered after regeneration.