AbstractThe experimental synthesis of quintet [V(AIP)]2(μ‐C6H6) and septet [Cr(AIP)]2(μ‐C6H6) analogues provide a new strategy to produce high spin multiplicity by utilizing inverse sandwiches. Aiming to design higher spin multiplicity, [M(AIP)]2(μ‐C4H4) (M = Cr, V) using C4H4 as central ligand are theoretically proposed. For [V(AIP)]2(μ‐C4H4), the most stable isomer group contains the septet and the open‐shell singlet isomers, which have three unpaired electrons on each V atoms. For [Cr(AIP)]2(μ‐C4H4), the most stable isomer group contains the septet and the nonet isomers, which have three and four unpaired electrons on each Cr atoms, respectively. The dissociation energies indicate that the above [M(AIP)]2(μ‐C4H4) are as stable as the available [M(AIP)]2(μ‐C6H6). It would be a reasonable strategy using C4H4 as central ligand to induce the higher spin multiplicity of inverse sandwiches.