Gas-fired boilers, gas stoves, and wall-mounted gas boilers are the main consumers of gas fuel, but they generally encounter problems when operating at high altitudes, such as reduced thermal efficiency and increased pollutant emissions. Previous studies on gas combustion characteristics under sub-atmospheric pressure were mostly carried out in a large space, which is quite different from chamber combustion equipment. Therefore, it is insufficient to guide the design and operation optimization of plateau gas equipment. In this paper, experimentations were carried out to explore the characteristics of a methane diffusion flame under sub-atmospheric pressures. The mass flow rates of methane and air remain consistent under different pressure conditions. The centerline temperature (Tc) distribution, flame appearance, smoke point, CO emission, and NOx emission under different pressures (ranging from 61.66 to 97.75 kPa) were examined under both fuel rich and lean conditions. The results show that Tc at the rear and front of furnace variation with pressure is opposite under fuel-lean and -rich combustion. The Tc at the front of furnace decreases with decreasing pressure, whereas Tc at the rear of furnace increases with decreasing pressure. With decreasing pressure, flame length decreases under lean combustion, but increases under rich combustion. The smoke point fuel flow rate, flame length, and residence time increases with decreasing pressure, following the law of negative exponent. The CO emission decreases with decreasing pressure, which indicates that the reduced pressure makes methane combustion more complete. For NO emission, the reduced pressure results in an opposite tendency under fuel-lean and -rich combustion. With decreasing pressure, the NO emission decreases under fuel-lean combustion but increases under fuel-rich combustion.