A realistic planar model of a silica-supported NiMo sulfide hydrotreating catalyst was used to study the intrinsic kinetics of thiophene hydrodesulfurization over a broad temperature range at atmospheric pressure. The specific nonporous nature of the model catalysts excludes possible diffusion limitations, which are commonly encountered in kinetic studies of their industrial porous analogues. The unique possibility to measure the intrinsic chemical kinetics over a large temperature range allowed us to observe a Volcano-type behavior for thiophene hydrodesulfurization. The specific kinetic parameters are discussed in terms of possible mechanisms.