The straightforward synthesis of the cationic, purely organometallic NiI salt [Ni(cod)2]+[Al(ORF)4]− was realized through a reaction between [Ni(cod)2] and Ag[Al(ORF)4] (cod=1,5‐cyclooctadiene). Crystal‐structure analysis and EPR, XANES, and cyclic voltammetry studies confirmed the presence of a homoleptic NiI olefin complex. Weak interactions between the metal center, the ligands, and the anion provide a good starting material for further cationic NiI complexes.