A composite material (MOF-5@AC) of MOF-5 and AC was successfully prepared. After characterization by a variety of means, it was shown that MOF-5 was covered on the surface of AC and existed in the form of microcrystals. A new micro-mesoporous pore appeared at 1.8–5 nm, while MOF-5 and AC are both microporous materials. And the thermal and water stability of MOF-5@AC is better than that of MOF-5. The adsorptive desulfurization experiment showed that the performance of the composite material was higher than that of the two parent materials, especially for the large molecular thiophenic sulfur compounds. And the reuse performance of MOF-5@AC after regeneration was also significantly improved compared the parent materials. The ratio of raw materials of composite materials plays an important role in the microstructure, morphology and desulfurization properties. After screening the ratio of raw materials, MOF-5@AC with a ratio of 1 : 5 showed the best desulfurization performance. The theoretical calculation results are in accordance with the desulfurization performance of the composite material (MOF-5@AC), which shows that MOF-5 is well dispersed on the AC surface and the pores are well exposed.