We report the redox, absorption, and emission characteristics of the tris(1,10-phenanthroline)ruthenium(II) complexes [Ru(phen)(3)](2+) bearing a (dimesityl)boryldurylethynyl (DBDE) charge-transfer (CT) unit at the 4 (4BRu(2+)) or 5 (5BRu(2+)) position of one of the three phen ligands. In acetonitrile at 298 K, 4BRu(2+) showed absorption and emission maximum wavelengths at 473 and 681 nm, respectively, which were shifted to longer wavelengths by 25 and 74 nm, respectively, compared with the relevant value of 5BRu(2+), 448 and 607 nm, respectively. The effects of a fluoride ion on the absorption and emission spectra of the complexes demonstrated that the CT interaction between the pi-electron system in the phen ligand (pi(aryl)) and the vacant p orbital on the boron atom (p(B)) in the DBDE group (i.e., pi(aryl)-p(B) CT) participated in the excited states of the complexes in addition to the Ru(II)-to-phen metal-to-ligand CT (MLCT) interaction. Reflecting such synergistic MLCT/pi(aryl)-p(B) CT, both 4BRu(2+) and 5BRu(2+) exhibited intense emission at 298 K with a quantum yield of 0.11. Furthermore, the emission lifetime of 4BRu(2+) was as long as 12 mu s and almost independent of the temperature (T=280-330 K). The present study indicated that the nonemissive dd excited triplet state did not participate to nonradiative decay in the MLCT excited triplet state of 4BRu(2+). The effects of the synergistic MLCT/pi(aryl)-p(B) CT interactions on the redox, absorption/emission, and photophysical characteristics of 4BRu(2+) and 5BRu(2+) are discussed in detail.