The synthesis and structural characterization of the hitherto unknown parent Co(bz)2+ (bz=benzene) complex and several of its derivatives are described. Their synthesis starts either from a CoCO5+ salt, or directly from Co2(CO)8 and a Ag+ salt. Stability and solubility of these complexes was achieved by using the weakly coordinating anions (WCAs) [Al(ORF)4]− and [F{Al(ORF)3}2]− {RF=C(CF3)3} and the solvent ortho‐difluorobenzene (o‐DFB). The magnetic properties of Co(bz)2+ were measured and compared in the condensed and gas phases. The weakly bound Co(o‐dfb)2+ salts are of particular interest for the preparation of further CoI salts, for example, the structurally characterized low‐coordinate 12 valence electron Co(PtBu3)2+ and Co(NHC)2+ salts.