The He I photoelectron spectra of M2(form)4 (M = Cr, Mo, W; form = N,N‘-diphenylformamidinate) and Mo2(cyform)4 (cyform = N,N‘−dicyclohexylformamidinate) are presented. For comparison, the Ne I, He I, and He II photoelectron spectra of Mo2(p-CH3-form)4 have also been obtained. The valence ionization features of these molecules are interpreted based on (1) the changes that occur with the metal and ligand substitutions, (2) the changes in photoelectron cross sections with excitation source, and (3) the changes from previously studied dimetal complexes. These photoelectron spectra are useful for revealing the effects that better electron donor ligands have on the valence electronic structure of M2(L⌒L)4 systems. Comparison with the He I spectra of the isoelectronic M2(O2CCH3)4 compounds is particularly revealing. Unlike with the more electron-withdrawing acetate ligand, several formamidinate-based ionizations derived from the nitrogen pπ orbitals occur among the metal−metal σ, π, and δ ionization bands. Alth...