Direct hydration of cyclohexene is considered to be the most promising process for the production of cyclohexanol due to its high atom economy and environmentally friendly. However, the low miscibility of cyclohexene and water leads to a low conversion of cyclohexene. Therefore, it is crucial to develop an efficient interfacial catalyst for the direct hydration of cyclohexene. In this work, cheap and environmentally friendly methyltrichlorosilane (MTCS) was used to modify the surface of HZSM-5 and create an amphiphilic HZSM-5 catalyst. The characterization results showed successful introduction of MTCS into HZSM-5 and an amphiphilic surface was formed on the catalyst 3MTCS-HZSM-5. The reaction results showed that catalyst 3MTCS-HZSM-5 with an amphiphilic surface exhibited the highest cyclohexene conversion by reducing the mass transfer resistance between the reactants and the catalyst. However, excessive introduction of organosilane on ZSM-5 not only constructs a hydrophobic surface but also covers most of the active acid sites, leading to a low catalytic activity.