We have investigated the steady-state and time-resolved optical properties of a family of linear Cu I complexes bearing structurally and electronically distinct mesoionic carbenes and amido ligands. By manipulating the electronic properties of the two ligands, we were able to modulate the emission mechanism of the different complexes, which were rationalized by both experimental measurements and vibrationally-resolved TD-DFT calculations. Complexes bearing a naphthyl substituted carbene, namely Cu Mes MIC Naph Cz, Cu Mes MIC Naph NPh2, and Cu 3,5-MePh MIC Naph Cz displayed LE emission after photoexcitation. In contrast, Cu Mes MIC p- An Cz, Cu Mes MIC 3,5-CF3Ph Cz, and Cu Mes MIC NPh2 display emission spectra that are consistent with excited states of LLCT character. The choice of ligands also affects the PL, resulting in generally poorly emissive complexes with PL ranging between 2.1 to 13.5%. The PL decays show multiexponential kinetics with prompt fluorescence lifetimes ranging 5.0 to 6.1 ns and phosphorescence lifetimes ranging from 3.1 to 12 ms. In the case of Cu Mes MIC 3,5-CF3Ph Cz a much shorter decay of 3.1 µs, probably due to TADF is observed. This work demonstrates how judicious variation of the electronic and structural properties of both ligands in linear Cu(I) MIC-based complexes can lead to switchable emission mechanisms.