Dehydrogenation of methylcyclohexane (MCH) was conducted over Pt/TiO2-Al2O3 catalysts, showing high activity, selectivity, stability, and high mechanical strength. XPS measurements revealed that the binding energy of Pt 4d(5/2) shifted to a lower energy by adding TiO2 due to electron donation from TiO2. Formed toluene released immediately on electron-rich Pt before further decomposition to form methane and coke thanks to pi-coordination. This phenomenon improved the catalytic performance, ensuring high selectivity, and durability for methylcyclohexane dehydrogenation.