In order to guide the application of hydrogen/methane mixture as fuel, explosion experiments were carried out using a cylindrical closed vessel with an inner diameter and length of 300 mm. The effects of hydrogen fraction (XH2) from 0 to 100% and equivalence ratio (Φ) from 0.6 to 1.4 on the flame evolution and explosion pressure were investigated. Meanwhile, CHEMKIN software was introduced to analyze the laminar burning velocity and sensitivity coefficient of the H2-CH4-air premixed gas. The results showed that, for a certain Φ, the maximum explosion pressure (pmax), the maximum pressure rise rate ((dp/dt)max), the explosion index (KG), and the laminar burning velocity increased monotonically with the increase of XH2. The duration to reach pmax and (dp/dt)max , named tA and tB, respectively, decreased gradually. After ignition, the flame surface gradually transformed from a smooth structure to a honeycomb flame lattice structure. With a constant Φ andan increasing XH2, the duration from ignition to the termination of the explosion decreased dramatically. Meanwhile, at the same moment the flame radius increased but the fold on the flame surface increased. The simulation results showed that the elementary reactions R35 and R52 had the most significant influence on the laminar burning velocity. The maximum molar fractions of the key radicals (H, O, and OH) had a positive correlation with the laminar burning velocity, and the increase of XH2 lead to a significant increase in the maximum molar fractions of the key radicals. The primitive reactions R38 and R84 were the dominant reactions affecting the rate of production (ROP) of key radicals.