MoS 2 catalysts were synthesized by hydrothermal method using ammonium heptamolybdate and thiocarbamide as materials, focusing on the effects of the addition of surfactants (such as hexadecyltrimethylammonium bromide, polyvinylpyrrolidone, and sodium lauryl benzenesulfate) during the MoS 2 catalyst preparation on their structure and activity in the hydrodeoxygenation (HDO) of 4-methylphenol. The addition of surfactant not only increased the surface area of MoS 2, but also changed its microstructure in the stack layer. Compared with Mo—S prepared without any surfactant, Mo—S—DB, Mo—S—CT, and Mo—S—PV exhibited higher activity in the HDO of 4-methylphenol. According to the characterization and catalytic activity results, the structure–activity relation was revealed, and the HDO mechanism of 4-methylphenol on these catalysts was well illustrated by the Rim–Edge model. The HDO of 4-methylphenol on these MoS 2 catalysts proceeded with two parallel routes (HYD and DDO), and their selectivity depended on its layer number in the stacks.