Reduction of N₂O to N₂ gas is currently of interest due to the deleterious effect of N₂O both as a greenhouse gas and as the greatest contributor to the stratospheric ozone depletion. N₂O being an inert molecule, its electrochemical reduction (deoxygenation) requires the implementation of catalytic processes. We will show that reduced forms of rhenium bipyridyl carbonyl complexes are selective catalysts for deoxygenation of nitrous oxide in organic medium in the presence of water (proton source). Cyclic voltammetry analysis indicates that Re complexes are first reduced to produce the catalytic active species, then N₂O binds to the reduced metal center and the resulting adduct is further reduced to trigger N-O bond breaking leading to N₂. This proposed mechanism is further assessed by forming the catalytically active state of rhenium complexes by two sequential one electron reductions followed by addition of N₂O(g), and monitoring the reaction kinetics by IR and UV-VIS spectroelectrochemical measurements. Then comparing this mechanism with the one taking place with aromatic organic catalysts, having reversible redox systems, we will emphasize differences between chemical (innersphere) vs. redox (outersphere) catalysis.