He I and He II gas-phase photoelectron spectra of Rh-2(O2CCF3)(4) are reported. The electron configuration of the metal-metal bond of Rh-2(O2CCF3)(4) is determined to be sigma(2) pi(4) delta(2) delta*(2) pi*(4) with an ionization energy order of sigma approximate to pi > delta > delta* approximate to pi*. The delta* and pi* ionization energies are similar within the range of vibrational energy separations. Assignment of the Rh-Rh delta ionization is assisted by previous observations that ionizations from delta orbitals in M-2(O2CCF3)(4) (M = Mo. W) and Mo-2(O2CH)(4) show enhanced intensity over ionizations from the sigma and pi orbitals with He II excitation. Changes in ionization energies from the dimolybdenum molecule to the dirhodium molecule and changes in ionization intensities from He I to He II excitation indicate greater metal-ligand mixing in these molecules than observed in other dimetal tetracarboxylates. Amsterdam density functional calculations agree with the observation that the Rh-Rh delta* and pi* energies are similar. The calculations also indicate substantial ligand mixing into the metal-metal sigma and pi orbitals. which is enhanced by the trifluoroacetate Ligand despite the inductive withdrawal of electron density by the electronegative fluorine atoms. It is found that a specific set of ligand orbitals that possess the same symmetries as the Rh-Rh sigma and pi orbitals are destabilized by overlap interactions with the filled fluorine p orbitals, resulting in greater metal-ligand mixing among these orbitals. The increased mixing explains the long-observed enhancement of the delta and delta* ionizations from He I to He II excitation for a number of M-2(O2CCF3)(4) (M = Mo. W. Ru) systems.