To construct more desirable adsorption affinity between the current metal–organic frameworks and benzothiophene (BT), a novel desulfurizer (V/Cu–BTC, where BTC represents 1,3,5-benzenetricarboxylic acid) was prepared by reducing Cu­(II) to Cu­(I) with V­(III) on Cu–BTC using a hydrothermal synthesis method. Using nitrogen adsorption–desorption, powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, we approved that the modifications of those novel desulfurizers have been successfully realized and further compared their structural changes. The BT capture performance from the different simulated fuels with V/Cu–BTC was evaluated by batch tests. The results manifest that V/Cu–BTC exhibited impressive desulfurization capacity, which is grander to Cu–BTC and some other adsorbents reported previously. Additionally, as a result of sieving and inertia mechanisms, this adsorbent possessed an extremely high affinity for BT capture in the presence of benzene. V/Cu–BTC showed a remarkable stability in BT adsorption, maintaining more than 90% initial sulfur uptake capacity after 5 regeneration times. In general, the V/Cu–BTC material is very beneficial for the adsorptive removal of BT.