Pt supported on ordered mesoporous silica (KIT-6) catalyst was examined for the dehydrogenation of homocyclic liquid organic hydrogen carriers (LOHCs, 1: MCH, 2: hydrogenated biphenyl-based eutectic mixture (H-BPDM)) conditions. The longer pore-residence time of the MCH molecules in the 3D bicontinuous pore structure of the Pt/KIT-6 catalyst strongly affected the catalytic activity because a higher MCH concentration was achieved in the vicinity of the Pt active sites. Pt/KIT-6 catalyst exhibited a higher surface area, pore volume, and Pt dispersion with narrower particle size distribution (average Pt particle size: ~1.3 nm). Therefore, higher LOHC conversion with faster hydrogen production occurred, with a higher hydrogen selectivity over Pt/KIT-6 compared with Pt/SiO2 and Pt/Al2O3. Long-term experiment results indicated that the Pt/KIT-6 catalytic activity was stable over the reaction time than that of the other catalysts. No significant structural collapse occurred in KIT-6 during the dehydrogenation. Carbon coking was observed for all three samples.