Polymethoxy dimethyl ether (PODE) is a potential diesel alternative fuel. However, currently, most of the research on PODE is concentrated on the engine bench tests, and corresponding basic spray combustion research is few which restricts the improvement of its efficient and clean combustion performance in power plants. The property of hydroxyl groups is active, and the area where they exist in large quantities is usually considered a high-temperature reaction area. By measuring the hydroxyl spectral band, important parameters such as flame structure, combustion reaction location and heat release rate can be obtained. Environmental oxygen concentration has a great influence on flame structure, and it is also an important parameter in controlling combustion reaction rate and pollutant emission. Therefore, on an optical constant volume combustion bomb, firstly used the self-luminescence measurement of hydroxyl spectral band to research the effects of oxygen concentration (15%~80%) on the lift-off length of PODE spray flame, then the integral value of hydroxyl self-luminescence spectrum intensity was converted to the point value by using Abel inverse transformation method to research the effects of oxygen-enriched concentration (40%~80%) on the hydroxyl distribution of PODE spray flame. The results show that: as the oxygen concentration increases from 15% to 40%, the flame lift-off length of PODE decreases rapidly. But further increase to 80%, the flame lift-off length decreases gradually until it is unchanged; The flame lift-off length of PODE is significantly smaller than diesel under the same oxygen concentration. At the distribution feature surface of hydroxyl spectral after inversion, the high-intensity area of PODE hydroxyl spectral is mainly concentrated in the thin layer of the spray edge diffusion flame under oxygen-enriched conditions; Meanwhile, the significant increase in local temperature makes the hydroxyl spectral intensity reach the maximum near the downstream of the premixed reaction zone. With the increase of oxygen concentration, the high-intensity area of hydroxyl spectral gradually migrates to the upper and middle areas of the flame. Its distribution appears to be shorter in the axial direction and narrower in the radial direction. When the flame reaches a quasi-steady state, compared with 40% oxygen concentration, the spectral intensity of hydroxyl at 60% and 80% oxygen concentration is significantly weaker in the middle and lower reaches of the flame, which indicates that the high concentration area of fuel upstream of the spray is more quickly to participate in the intense combustion reaction.