A series of six luminescent two-coordinate Cu(I) complexes were investigated bearing nonconventional N-heterocyclic carbene ligands, monoamido-aminocarbene (MAC*) and diamidocarbene (DAC*), along with carbazolyl (Cz) as well as mono- and dicyano-substituted Cz derivatives. The emission color can be systematically varied over 270 nm, from violet to red, through proper choice of the acceptor (carbene) and donor (carbazolyl) groups. The compounds exhibit photoluminescent quantum efficiencies up to 100% in fluid solution and polystyrene films with short decay lifetimes (tau approximate to 1 mu s). The radiative rate constants for the Cu(I) complexes (k(r) = 10(5)-10(6) s(-1)) are comparable to state of the art phosphorescent emitters with noble metals such as Ir and Pt. All complexes show strong solvatochromism due to the large dipole moment of the ground states and the transition dipole moment that is in the opposite direction. Temperature-dependent studies of (MAC*)Cu(Cz) reveal a small energy separation between the lowest singlet and triplet states (Delta ES1-T1 = 500 cm(-1)) and an exceptionally large zero-field splitting (ZFS = 85 cm(-1)). Organic light-emitting diodes (OLEDs) fabricated with (MAC*)Cu(Cz) as a green emissive dopant have high external quantum efficiencies (EQE = 19.4%) and brightness of 54 000 cd/m(2) with modest roll-off at high currents. The complex can also serve as a neat emissive layer to make highly efficient OLEDs (EQE = 16.3%).