Abstract: Oxygen (O₂) is essential for life support and rocket propulsion in Mars exploration missions, and in situ oxygen production from the Martian atmosphere is of profound scientific and engineering significance. In this article, we propose a novel method for O₂ production from the Martian atmosphere by using glow discharge ionization combined with a self-developed oxygen-permeable membrane (OPM). Experiments under simulated Martian atmospheric conditions examined parameter impacts on the O₂ production rate and assessed the operating characteristics and glow discharge plasma tolerance of the OPM. Results indicate that (1) the proportion of O₂ produced positively correlates with the ionization voltage under fixed discharge electrode spacing, pressure, and flow rate, reaching a maximum of 8.18% (saturating at 4600–5400 V); (2) O₂ yield rises with the carbon dioxide (CO₂) flow rate at a constant pressure, with the maximum value reaching 0.5 g/h; (3) titanium (Ti) and molybdenum (Mo) electrodes exhibit higher application potential under high voltage conditions; (4) the OPM operates at temperatures above 800°C and shows few changes in the main body sections after 24 h of plasma tolerance testing. This study lays the foundation for future development of a mature Mars oxygen production prototype with lower energy consumption and higher efficiency.