A series of (carbene)Au-(I)(aryl) complexes are reported. The nature of the lowest excited state in these complexes changes character from metal-to-ligand charge transfer (MLCT) to interligand charge transfer (ICT) with increasing electron-donating strength of the aryl ligand. Complexes that have the MLCT lowest excited state undergo a Renner-Teller bending distortion upon excitation. Such a distortion leads to a large rate of nonradiative decay, on the order of 10(8) s(-1). Renner-Teller-based nonradiative decay does not occur in chromophores with an ICT emissive state. Introducing a julolidine moiety and ortho-methyl substituents to the aryl group makes the molecule rigid and hinders the rotation along the Au-C-aryl-coordinate bond. Consequently, the nonradiative decay rates of these ICT emitters are decreased and become lower than the radiative decay rate constants (k(r) = 10(5) s(-1)). Thus, high-luminescent efficiencies (Phi(PL) = 0.61 and 0.77) along with short lifetimes (tau < 2 mu s) are obtained for yellow and green emitters, respectively. Thermally assisted delayed fluorescence behavior is observed, owing to the small exchange energy (Delta E-ST < 1600 cm(-1)) in these emitters.