Selective C-C and C-H bond activations are an important catalytic process to produce various value-added hydrocarbons via reforming processes. For producing desired product with a high yield, control of reaction pathway through the design of catalyst and fundamental understanding and clarification of reaction mechanism are prerequisite. In this work, we designed heterogeneous catalysts by combining Pt nanoparticles and two different mesoporous zeolites with microporous frameworks of BEA and MFI for the hydrogenative model reforming reaction of hydrocarbon (i.e., methylcyclopentane). Depending on the catalyst combination, the reaction pathways of (i) dehydrogenation, (ii) ring-opening with isomerization, and ring-enlargement with (iii) hydrogenation and (iv) dehydrogenation of C5-cyclic ring to C6-cyclic ring (i.e., cyclohexane and benzene) can be controlled to produce various products with high yields. Furthermore, we revealed a reaction intermediate formed at the interface of Pt and zeolite by real-time surface vibrational sum-frequency generation spectroscopic studies. This study would provide practical and fundamental insights for design of heterogeneous catalyst for controlling reaction pathways.