The synthesis and photophysical properties of two new Re(]) complexes are reported: fac-Re(phenC≡ CH)(CO)(3)Cl (where phenC≡ CH is 5-ethynyl-1,10-phenanthroline) and its Au(l)-acetylide analogue (fac-Re(phenC≡ CAuPPh3CO)(3)(-) Cl). Also reported are the photophysical measurements obtained for the benchmark fac-Re(phen)(CO)(3)Cl chromophore, as well as the phenC≡ CAuPPh3 and phenC≡ CH ligands. The unstable nature of the precursor gold-containing ligand illustrates the advantage of using the "chemistry on the complex" approach, which facilitated preparation of the Re-Au binuclear complex. Where possible, all compounds were studied by static and transient absorption (TA), as well as steady-state and time-resolved photoluminescence (TRPL), at room temperature (RT) and 77 K, as well as nanosecond time-resolved infrared (TRIR) spectroscopy. The spectroscopic information provided by these techniques enabled a thorough evaluation of excited-state decay in most cases. In fac-Re(phenC≡ CH)(CO)(3)Cl, the RT excited-state decay is most consistent with a metal-to-ligand charge transfer (MLCT) assignment, whereas at 77 K, the lowest excited state is dominated by the triplet intraligand ((IL)-I-3) state, localized within the diimine ligand. The lowest excited state in fac-Re(phenC≡ CAuPPh3)(CO)(3)Cl seems to result from an admixture of Re-based MLCT and (IL)-I-3 states resident on the phenC≡ CAuPPh3 moiety. TA and TRIR methods indicate that these excited states are thermally equilibrated at room temperature, At 77 K, the MLCT energy of fac-Re(phenC≡ CAuPPh3)CO)(3)Cl is increased as a result of the glassy medium and the resulting excited state can be considered to be ligand-localized.