With the aid of density function theory, the molecular and electronic structures of the molecules Mo2(O2CMe)4, MoW(O2CMe)4, and W2(O2CMe) 4 and their single-electron oxidized radical cations have been determined; this includes calculated observables such as v(MM) and the δ → δ* electronic transition energies. The calculated properties are compared with those for the corresponding pivalates, M2(O 2CtBu)4 (M = Mo or W) and MoW(O 2CtBu)4 and their radical cations prepared in situ by oxidation with Cp2FePF6. The EPR spectra of the radical cations are also reported. The EPR spectrum of the MoW(O 2CtBu)4+ cation reveals that the unpaired electron is in a polarized MM δ orbital having 70% Mo and 30% W character. The MM stretching frequencies show good correlation with the MM bond lengths obtained from single-crystal X-ray diffraction studies of MoW(O 2CtBu)4, W2(O2C tBu)4, and W2(O2C tBu)4+PF6- compounds, along with previously reported structures. These data provide benchmark parameters for valence trapped dicarboxylate bridged radical cations of the type [(tBuCO2)3M2]2(μ- O2C-X-CO2)+ (X = conjugated spacer).