A nickel complex incorporating an N2O ligand with a rare η2‐N,N’‐coordination mode was isolated and characterized by X‐ray crystallography, as well as by IR and solid‐state NMR augmented by 15N‐labeling experiments. The isoelectronic nickel CO2 complex reported for comparison features a very similar solid‐state structure. Computational studies revealed that η2‐N2O binds to nickel slightly stronger than η2‐CO2 in this case, and comparably to or slightly stronger than η2‐CO2 to transition metals in general. Comparable transition state energies for the formation of isomeric η2‐N,N’‐ and η2‐N,O‐complexes, and a negligible activation barrier for the decomposition of the latter likely account for the limited stability of the N2O complex.