Adsorptive desulfurization is one of the alternative technologies for the effective removal of sulfides from fuels. Functionalization of metal-organic frameworks (MOFs) with Cu⁺ is extremely desirable for adsorption separation via π-complexation interaction with adsorbed molecules. Here we report that Cu⁺ cation is significant and highly effective for adsorption desulfurization in a new type of Cu⁺- modified UiO-66(Zr). First, Cu²⁺ was introduced via ion-exchange with H⁺ of UiO-66-SO₃H. Then, Cu⁺ cation was obtained from the reduction of Cu²⁺ by using vapor-induced reduction, in which vapors of reducing agents diffuse into the pores of MOFs at a lower temperature. The resulted UiO-66-SO₃Cu(I)− 0.15 has a better adsorption capacity for thiophene compared to pure UiO-66. In the presence of toluene, the UiO-66-SO₃Cu(I)− 0.15 also exhibits high adsorption capacity for thiophene. After recycling four times, UiO-66-SO₃Cu(I)− 0.15 still remains a high adsorption capacity.