Four mononuclear Cu(I) complexes were prepared, described as [Cu(N,N)(2)]PF6 (1) and [Cu(N, N)(P,P)] PF6 (2-4), where N, N is N-(1-(2H-indazol-2-yl)ethylidene)-2,6-diisopropylaniline and P, P are phosphine derived ancillary ligands (bis[2-(diphenylphosphino) phenyl] ether (POP), bis(diphenylphosphino) ethane (dppe) or 2 PPh3). These new species were characterized by NMR, FT-IR, elemental analyses, cyclic voltammetry, UV-Vis - emission spectroscopy, transient absorption spectroscopy and DFT calculations. In addition, complexes 1 and 2 were characterized by X-ray diffraction. The four complexes showed an MLCT absorption band between 400 and 450 nm, in addition to a weakly structured phosphorescence in a 4 : 1 ethanol : methanol glassy matrix at 77 K. Complexes 2-4 have emission profiles that resemble the phosphorescence of the protonated N, N ligand, suggesting a triplet LC character of the lowest lying excited state at 77 K. By contrast, a mixed MLCT/LC triplet emission is most likely responsible for the phosphorescence in complex 1. Weak ligand-centered emission is also detected in the solid state at room temperature but only in the case of complexes 2 and 4, suggesting thermally activated deactivation processes in the case of 1 and 3. Notably, the transient absorption spectroscopy of complexes 2-4 in CH2Cl2 solution confirms a strong contribution from a ligand-centered (LC) triplet excited state, pointing towards a mixed (MLCT)-M-3/(LC)-L-3 character of the transient species in solution at room temperature, undergoing a non-radiative deactivation in the mu s time-scale. This behavior markedly differs from that observed for complex 1, whose short-lived (MLCT)-M-3 excited state is followed by ultrafast transient absorption spectroscopy.