In addition to serving as an important energy carrier, hydrogen storage material also has the potential to be used as an effective solid reducing agent. This paper is concerned with the application of MgH2/MoS2 hydrogen storage materials to thiophene desulfurization through catalytic transfer hydrogenation. The hydrogen content of the as-prepared MgH2/MoS2 composites is determined to be 6.15 wt% with a dehydrogenation peak temperature of 402 °C. Taking MgH2 as hydrogen donor, thiophene hydrodesulfurization has taken place at atmospheric pressure and at the temperature lower than the onset desorption temperature, indicating that a coupling effect occurs between MgH2 decomposition and thiophene hydrogenation. It is further revealed that sulfur removal in thiophene under the studied condition preferentially proceeds via direct desulfurization (DDS) route. Our density functional theory (DFT) calculations manifest that energy barriers of the minimum energy path for thiophene hydrodesulfurization are all <1.35 eV. This exploratory case study demonstrates the feasibility of catalytic transfer hydrogenation using solid-state hydrogen storage materials.