Herein we report a series of charged iridium complexes emitting from near-UV to red using carbene-based N⁁C: ancillary ligands. Synthesis, photophysical and electrochemical properties of this series are described in detail together with X-ray crystal structures. Density Functional Theory calculations show that the emission originates from the cyclometallated main ligand, in contrast to commonly designed charged complexes using bidentate N⁁N ancillary ligands, where the emission originates from the ancillary N⁁N ligand. The radiative process of this series of compounds is characterized by relatively low photoluminescence quantum yields in solution that is ascribed to non-radiative deactivation of the excited state by thermally accessible metal-centered states. Despite the poor photophysical properties of this series of complexes in solution, electroluminescent emission from the bluish-green to orange region of the visible spectrum is obtained when they are used as active compounds in light-emitting electrochemical cells.