Nitrous oxide (N2O), a widespread greenhouse gas, is a thermodynamically potent and environmentally green oxidant that is an attractive target for activation by metal centers. However, N2O remains underutilized owing to its high kinetic stability, and the poor ligand properties of this molecule have made well-characterized metal-N2O complexes a rarity. We now report a vanadium-pyrrolide system that reversibly binds N2O at room temperature and provide the first single-crystal X-ray structure of such a complex. Further characterization by vibrational spectroscopy and DFT calculations strongly favor assignment as a linear, N-bound metal-N2O complex.