Hydrodesulfurization is well established in the industry while costly and environmentally unfriendly due to CO₂ emissions and H₂S production. An alternative, cost-effective desulfurization process remains unreported. Here, we demonstrate a desulfurization process for dibenzothiophene, one of the most well-known and recalcitrant sulfur-containing model compounds against catalytic desulfurization, under the regulation of methane instead of hydrogen over a combination of two catalysts, generating a new sulfur-containing product, CS₂, as an important intermediate in organic chemistry and non-polar solvent with lower environmental impact than H₂S. A catalytic mechanism is proposed and supported by extensive experimental and computational evidence. It is discovered that methane acts as a critical initiator and intensifies the direct desulfurization pathway, where two catalysts must work cooperatively and a surface sulfur transfer process is indispensable. This study explores an alternative desulfurization route with unique reaction pathways towards CS₂ formation, whose practical potential is also supported by the desulfurization performance over a series of real-world crude samples.