Here, we describe the synthesis, photophysical properties, electrochemistry, and computational study of a series of Cu I complexes containing co-planar MIC and carbazolide ligands. Through variations of the sterics and electronics of the substituents on the carbene ligand, we observed different contributions to the emission from the LLCT and LE states (Figure ). Notably, however, the LE emission originates from the carbene as opposed to the carbazolide ligand as was reported by Li et al., as evidenced by our variable temperature and time-resolved PL measurements, supported by the theoretical calculations.