A novel two-step synthetic strategy, based on a silver-assisted cyclometalation reaction with IrCl3, allows the preparation of the first cationic Ir(III) complexes with tetrazole units on the C^^N cyclometallating ligand. Three of them exhibit high PLQY in solution and in the solid state (55−70%) and the highest-energy MLCT/LLCT emission bands ever reported among cationic iridium complexes without fluorine residues on the cyclometalated ligands. A comprehensive study, from theoretical calculations to LEC devices, is presented.