The gas‐phase reactions between Ni⁺ (²D_5/2) and aminoacetonitrile, a molecule of prebiological interest as possible precursor of glycine, have been investigated by means of mass spectrometry techniques. The mass‐analyzed ion kinetic energy (MIKE) spectrum reveals that the adduct ions [NC-CH₂-NH₂, Ni⁺] spontaneously decompose by loosing HCN, H₂, and H₂CNH, the loss of hydrogen cyanide being clearly dominant. The structures and bonding characteristics of the aminoacetonitrile–Ni⁺ complexes as well as the different stationary points of the corresponding potential energy surface (PES) have been theoretically studied by density functional theory (DFT) calculations carried out at B3LYP/6‐311G(d,p) level. A cyclic intermediate, in which Ni⁺ is bisligated to the cyano and the amino group, plays an important role in the unimolecular reactivity of these ions, because it is the precursor for the observed losses of HCN and H₂CNH. In all mechanisms associated with the loss of H₂, the metal acts as hydrogen carrier favoring the formation of the H₂ molecule. The estimated bond dissociation energy of aminoacetonitrile–Ni⁺ complexes (291 kJ mol⁻¹) is larger than those measured for other nitrogen bases such as pyridine or pyrimidine and only slightly smaller than that of adenine.