A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO)(3)(CdropC-C6H4-CdropC)Fe(C5Me5)(dppe)], 1, and its oxidized species, [Re(bpy)(CO)(3)(CdropC-C6H4-CdropC)Fe(C5Me5)(dppe)][PF6], 2, have been synthesized and their X-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO)(3)(CdropC-C6H4-(H)C=C)Fe-(C5Me5)(dppe)][PF6], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at -1.49 V (vs SCE), a fully reversible oxidation at -0.19 V, and a quasireversible oxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen- substituted model complex Re(bpy)(CO)(3)(CdropC-C6H4-CdropC)Fe(C5H5)(dHpe) (Cp = C5H5, dHpe=H2P-(CH2)(2)-PH2) (1-H) show that the LUMO is mainly bipyridine ligand pi(*) in character while the HOMO is largely iron(II) d orbital in character. The electronic absorption spectrum of 1 shows low-energy absorption at 390 nm with a 420 nm shoulder in CH2Cl2, while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additional low-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(l)-alkynyl complex [Re(bpy)(CO)(3)(CdropC-C6H4-CdropC-H)], 4, complex 1 is found to be nonemissive, and such a phenomenon is attributed to an intramolecular quenching of the emissive dpi(Re) --> pi(*)(bpy) (MLCT)-M-3 state by the low-lying MLCT and LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from the dpi(Re) --> pi(*)(bpy) (MLCT)-M-3 state can be demonstrated in the oxidized species 2 and the related vinylidene analogue 3 due to the absence of the quenching pathway.