To investigate the flame propagation characteristics and chemical kinetics of premixed propane/hydrogen/air mixtures at elevated pressure, a series of experiments on propane/hydrogen/air mixtures with varying initial pressures (P0 = 100–300 kPa) and equivalence ratios (φ = 0.6–1.4) at a hydrogen fraction of 0.6 and an ambient temperature of 298 K were carried out in a closed duct with an aspect ratio of 15. The chemical kinetics of the elementary reaction were analyzed numerically. The results revealed that the combustion-induced rapid phase transition (cRPT) occurred in the premixed C3H8/H2/air flames. Both the combustion pressure and flame propagation velocity increase with initial pressure except at P0 = 300 kPa, where the flame propagation velocity decreases. Moreover, the linear dependence between the laminar burning velocity and peak mole fraction [H + O + OH]max was found by the effect of initial pressure on the peak mole fraction (H, O, OH). The explosion pressure Prea and the maximum rate of production of free radical H/O show excellent correlations. The maximum rate of pressure rise can be predicted by the maximum heat release rate (HHR). These results provide essential data on elevated-pressure duct accidents and have important implications for explosion prevention.