Methane/air is a widely used fuel. The effects of equivalent ratio (0.8–1.2) and initial pressure (1.0 atm–1.2 atm) on the flame propagation process and explosion overpressure of methane/air premixed gas were studied using a high-speed camera and pressure sensor in a rectangular closed container. Four flame modes in the late propagation stage are distinguished according to the different modes of secondary cup movement. The flame propagation velocity and structure evolution are analyzed by defining the characteristic times. The relationship between the flame structure evolution and the growth of flame propagation velocity and explosion overpressure is revealed. The results show that, in lean combustion, the maximum flame propagation velocity increases with initial pressure increase, and the explosion overpressure fluctuates more significantly. However, the opposite is true with fuel-rich combustion. The interaction between pressure waves and flame fronts can enhance the growth of explosion overpressure in fuel-rich combustion but can inhibit the growth in lean combustion. This work can provide more data support and reference for the application prospect and safe application of methane.