The permeation of oxygen through Ag0.05Zr over the temperature range of 300–650 °C under glow‐discharge conditions has been studied and compared to the permeation of thermally dissociated molecular oxygen. A low‐energy dc glow‐discharge in O2has been employed which produced approximately 10% atoms. The permeation rate during the glow discharge was found to be much higher (a factor of ∼10) than without the glow discharge. The small fraction of oxygen atoms generated appears to dominate the permeation because of much higher solution probabilities. Below 500 °C, the activation energy for the permeation with glow discharge was found to be 15.5 kcal/mol compared to 22.0 kcal/mol without glow discharge (molecular oxygen). Above 500 °C, the enhanced permeation with glow discharge gradually diminishes with increasing temperature and approaches that observed without the glow discharge at high temperature; the reason for this is primarily because of the thermal instability of the supersaturated high‐pressure interface where atoms recombine and desorb back into the gas phase.