Five mono/di/trinuclear iridium(III) complexes (1-5) bearing the carbazole-derivative-tethered 2-(quinolin-2-yl)quinoxaline (quqo) diimine (N<^>N) ligand were synthesized and characterized. The photophysical properties of these complexes and their corresponding diimine ligands were systematically studied via UV-vis absorption, emission, and transient absorption (TA) spectroscopy and simulated by time-dependent density functional theory. All complexes possessed strong well-resolved absorption bands at <400 nm that have predominant ligand-based (1)pi,pi* transitions and broad structureless charge-transfer ((CT)-C-1) absorption bands at 400-700 nm. The energies or intensities of these (CT)-C-1 bands varied pronouncedly when the number of tethered Ir(quqo)(piq)(2)(+) (piq refers to 1-phenylisoquinoline) units, pi conjugation of the carbazole derivative linker, or attachment positions on the carbazole linker were altered. All complexes were emissive at room temperature, with 1-3 showing near-IR (NIR) (MLCT)-M-3 (metal-to-ligand charge-transfer)/(LLCT)-L-3 (ligand-to-ligand charge-transfer) emission at similar to 710 nm and 4 and 5 exhibiting red or NIR (ILCT)-I-3 (intraligand charge-transfer)/(LMCT)-L-3 (ligand-to-metal charge-transfer) emission in CH2Cl2. In CH3CN, 1-3 displayed an additional emission band at ca. 590 nm ((ILCT)-I-3/(LMCT)-L-3/(MLCT)-M-3/(3)pi,pi** in nature) in addition to the 710 nm band. The different natures of the emitting states of 1-3 versus those of 4 and 5 also gave rise to different spectral features in their triplet TA spectra. It appears that the parentage and characteristics of the lowest triplet excited states in these complexes are mainly impacted by the R. systems of the bridging carbazole derivatives and essentially no interactions among the Ir(quqo)(piq),* units. In addition, all of the diimine ligands tethered by the carbazole derivatives displayed a dramatic solvatochromic effect in their emission due to the predominant intramolecular charge-transfer nature of their emitting states. Aggregation-enhanced emission was also observed from the mixed CH2Cl2/ethyl acetate or CH2Cl2/hexane solutions of these ligands.