We report the synthesis and photophysical/photoredox characteristics of a novel tricarbonyl rhenium(1) complex having a (dimesityl)boryldurylethynyl (DBDE) group at the 4-position of a 1,10-phenanthroline (phen) ligand, [Re(CO)(3)(4-DBDE-phen)Br] (ReB). ReB in tetrahydrofuran at 298 K showed the metal-to-ligand charge transfer (MLCT) emission at around 681 nm with the lifetime (tau(em)) of 900 ns. The relatively long emission lifetime of ReB compared with that of [Re(CO)(3)(phen)Br] (RePhen, tau(em) = 390 ns) was discussed on the basis of the temperature dependent tau(em) and Franck-Condon analysis of the emission spectra of the two complexes. Emission quenching studies of both ReB and RePhen by a series of electron donors revealed that the photoinduced electron transfer (PET) quenching rate constant of ReB was faster than that of RePhen at a given Gibbs free energy change of the PET reaction (Delta G(ET)(0) > -0.5 eV). All of the results on ReB were discussed in terms of the contribution of the CT interaction between the pi-orbital(s) of the aryl group(s) and the vacant p-orbital on the boron atom in DBDE to the MLCT state of the complex.