The ligand-to-metal charge transfer state (LMCT) of (dmpe)3Re2+ (dmpe = 1,2-bis­(dimethylphosphino)­ethane) has been demonstrated to be a potent oxidant (E 0(Re2+*/Re+) = 2.61 V vs standard calomel electrode). This complex has been traditionally prepared by nontrivial routes in low yields, and very little has been achieved in optimizing the ground state and emission energy properties of the general class of complexes (PP)3Re2+ (PP = chelating diphosphine) through phosphine modification. Improved syntheses for Re­(I) tris-homoleptic diphosphine complexes (PP)3Re+ (PP = 1,2-bis­(dimethylphosphino)­ethane (dmpe), 1,2-bis­(diethylphosphino)­ethane (depe), bis­(dimethylphosphino)­methane (dmpm), bis­(diphenylphosphino)­methane (dppm), Me2PCH2PPh2, 1,3-bis­(dimethylphosphino)­propane (dmpp), or 1,2-bis­(dimethyl-phosphino)­benzene (dmpb)) were achieved by single-pot reactions exploiting the reducing potential of the phosphines when reacted with ReV oxo-complexes in 1,2-dichlorobenzene at 160–180 °C. Single-electron chemical oxidation of (PP)3Re+ yields luminescent ReII analogues; appropriate use of Ph3C+, Cp2Fe+, or (4-BrC6H4)3N+ B­(C6F5)4 – salts produced (PP)3Re2+ complexes in good yields. Crystallographic trends for the Re+/Re2+ pairs show significantly lengthened Re2+–P bonds for (PP)3Re2+ relative to the corresponding (PP)3Re+ system. The redox and luminescence behavior of the complexes indicates the luminescence is from a ligand P­(σ)-to-metal (Re­(dπ)) charge transfer (2LMCT) state for all the complexes. Structured luminescence at 77 K is postulated to originate from relaxation of the 2LMCT state into two spin–orbit coupled states: the ground state and a state ∼3000 cm–1 above the ground state. The excited-state reduction potential (Re­(II*/I)) for (depe)3Re2+ was determined from the free energy dependence of luminescence quenching rate constants. Yields for formation of charge separated ions were determined for three of the complexes with a variety of electron donors. Despite favorable electrostatics, no charge separated ions were observed for radical ion pairs for which the energy of back electron transfer exceeded 1.1 V.