The reaction of aminoacrylonitrile, a species of astrochemical interest, with Ni(+)((2)D(5/2)) was investigated by means of mass spectrometry techniques and density functional theory calculations. The dominant fragmentations in the MIKE spectrum correspond to the loss of [C2,N,H3], HCN, and NH3, the loss of H2 being very minor. The structure and bonding of the different aminoacrylonitrile-Ni(+) complexes were investigated at the B3LYP/6-311G(d,p) level of theory. The same approach was employed in our survey of the corresponding potential energy surface. This survey indicates that the [C2,N,H3] neutral product can be formed either as ketenimine (CH2CNH) or acetonitrile. The formation of the latter is significantly more exothermic but involves slightly higher activation barriers; so very likely, both isomers are produced along the reaction process. The lost of HNC is not competitive with the loss of HCN, because when the former is formed the products lie higher in energy and the corresponding mechanisms involve energy barriers above the entrance channel. The loss of NH3 is associated with the formation of a complex between cyanoacetylene, HCCCN, which is very abundant in the interstellar media, and Ni(+).