To gain insights into the trends in metal–metal multiple bonding among the Group 6 elements, density functional theory has been employed in combination with multiconfigurational methods (CASSCF and CASPT2) to investigate a selection of bimetallic, multiply bonded compounds. For the compound [Ar-MM-Ar] (Ar=2,6-(C₆H₅)₂-C₆H₃, M=Cr, Mo, W) the effect of the Ar ligand on the M₂ core has been compared with the analogous [Ph-MM-Ph] (Ph=phenyl, M=Cr, Mo, W) compounds. A set of [M₂(dpa)₄] (dpa=2,2′-dipyridylamide, M=Cr, Mo, W, U) compounds has also been investigated. All of the compounds studied here show important multiconfigurational behavior. For the Mo₂ and W₂ compounds, the σ²Ï€⁴δ² configuration dominates the ground-state wavefunction, contributing at least 75 %. The Cr₂ compounds show a more nuanced electronic structure, with many configurations contributing to the ground state. For the Cr, Mo, and W compounds the electronic absorption spectra have been studied, combining density functional theory and multireference methods to make absorption feature assignments. In all cases, the main features observed in the visible spectra may be assigned as charge-transfer bands. For all compounds investigated the Mayer bond order (MBO) and the effective bond order (EBO) were calculated by density functional theory and CASSCF methods, respectively. The MBO and EBO values share a similar trend toward higher values at shorter normalized metal–metal bond lengths.