Ethyl mercaptan (Et‐SH) is a common sulfide in natural gas. It is toxic and can cause equipment corrosion and catalyst poisoning, which needs to be properly handled. In present paper, Zn−Ti layered double hydroxide and its nanosheets were prepared by hydrothermal method and solvothermal method using ethylene glycol (EG) as a reaction medium, respectively. The desulfurization capabilities of the as‐prepared samples were evaluated through the adsorption of Et‐SH from methane gas. The results show that the desulfurization performance of the samples prepared by solvothermal method is significantly elevated comparing that of sample prepared by hydrothermal method. The washing solvent in the post‐treatment of the samples obtained by solvothermal method has great influence on its desulfurization performance. Density Functional Theory (DFT) calculations indicate that the H atom of hydroxyl group on the surface of nanosheet is the main active site for adsorption of Et‐SH. The strong hybridization between S 3p orbitals and H 1s orbitals promote the formation of S⋅⋅⋅H bond.