AbstractCompared to conventional heterogeneous catalysis, membrane catalysis can facilitate in situ removal of inhibiting species on a catalyst, therefore effectively increases the reaction rate. Herein, kinetically controlled decomposition of N2O was studied employing a La0.2Sr0.8Ti0.2Fe0.8O3–δ (LSTF) perovskite membrane, and the direct catalytic N2O decomposition over membrane surface was compared with membrane catalysis of N2O decomposition involving in situ oxygen removal. In the case of membrane catalysis, oxygen produced from N2O conversion can be in situ removed by using a LSTF oxygen‐permeable membrane, thus increasing the amount of surface active sites for N2O decomposition. By sweeping hydrogen at one side of the membrane to consume the permeated oxygen from the other side N2O conversion was improved.