Density functional theory has been used to explore possible homoleptic binuclear Cr carbonyls Cr2(CO)n (n = 11, 10, 9, and 8) using the pure DFT method BP86 and the hybrid Hartree–Fock DFT method B3LYP. The binuclear Cr2(CO)11 is computed to be thermodynamically unstable with respect to dissociation into mononuclear fragments in contrast to the experimentally known Cr2(CO)10(μ-H)−. This may account for the failure to synthesize Cr2(CO)11 as a stable compound. Optimized structures for the formally unsaturated Cr2(CO)10 are a singlet with two four-electron donor bridging CO groups and no formal metal–metal bonding and a triplet with no bridging CO groups and a CrCr double bond similar to the OO bond in O2. The more highly unsaturated homoleptic binuclear chromium carbonyls Cr2(CO)9 and Cr2(CO)8 are computed to be stable with respect to dissociation into mononuclear fragments in contrast to Cr2(CO)11 and Cr2(CO)10. The optimized structure for Cr2(CO)9 is a singlet Cr2(CO)6(μ-CO)3 with a short metal–metal distance (∼2.3 Å) consistent with the Cr≡Cr triple bond required for an 18-electron configuration for each Cr atom. The global minimum for Cr2(CO)8 is a closely related Cr2(CO)5(μ-CO)3 structure derived from the Cr2(CO)6(μ-CO)3 global minimum by loss of one of the terminal CO groups with little change in the Cr≡Cr distance. Higher energy minima for Cr2(CO)8 include two different Cr2(CO)6(μ-CO)2 structures, one formulated with two four-electron donor μ-CO groups bridging two Cr(CO)3 groups and the other with similar μ-CO groups bridging a Cr(CO)4 and a Cr(CO)2group.