The reaction of NiCl2•2H2O with acetamidoxime (MeC(NH2)=NOH) in the presence of PhCN in MeOH gave the cationic dimetallic complex [1]Cl4, bearing bridging O‐coordinated aminonitrone and chelating imidoylamidoxime ligands, derived from amidoxime‐PhCN coupling. The experimental data and theoretical calculations (M06/MDF10(Ni) and 6–31G*(other atoms) indicated that the aminonitrone form of amidoxime was stabilized only as a μ2‐O‐bridging ligand, whereas Noxime‐coordination was preferred rather than O‐coordination for monodentate‐coordinated amidoximes.